JP2001510728A - Fluid treatment - Google Patents

Abstract

  (57) [Summary] By contacting the fluid with an adsorbent (10) having a crystalline structure such as a SbSn intermetallic compound, the nucleophilic polar head (13) is attracted to the defect sites (12) on the adsorbent surface and becomes like sulfur. Treatment to remove undesirable chemical species.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD [0001] The present invention relates to the treatment of fluids to remove undesirable components, and more particularly, chemical species.

BACKGROUND OF THE INVENTION [0002] Treatment of such fluids is common in the hydrocarbon fuel processing industry, for example, in sulfur refinery removal. One method of such treatment is commonly referred to as a hydrotreating process that exposes the feedstock to high temperatures and pressures. This method requires a large energy input and is expensive.

Another method involving contacting the feedstock with an absorbent containing a metal such as sodium, potassium, barium or calcium is disclosed in European Patent EP
254781 (Chevron). EP 332324 (ICI) proposes removing hydrogen sulfide by passing a feedstock through a zinc oxide-containing adsorbent. This adsorbent can be regenerated using a gas stream containing water. Adsorption as a treatment method seems to be problematic in that it is only effective for gaseous feed streams and limits the feed stream throughput.

[0004] The present invention is therefore aimed at achieving a fluid treatment in a simpler way.

According to the present invention, a step of contacting a fluid containing an undesired chemical species with a filter having a surface crystal structure to facilitate adsorption of the undesired chemical species of the fluid to the filter. There is provided a method of treating a fluid having:

In one embodiment, the filter has a defect site on a surface adjacent to an electron-deficient atom. This provides a very effective adsorption mechanism. In one embodiment, the filter contains an intermetallic compound, and the intermetallic compound contains Sb and Sn.

[0007] In one embodiment, the fluid contains water. In certain embodiments, the fluid is a liquid and is an emulsion, preferably one of the emulsion phases is an electrolyte. Preferably, the emulsifier is a surfactant.

In one embodiment, the surfactant is of a type having a function of inverting a micelle containing a group containing a heterocyclic ring so as to orient the group outward. The surfactant is preferably of a type in which the hydrophobic group has a long chain and the hydrophilic group is carboxylate.

[0009] In another embodiment, a magnetic field is applied to bring the fluid into contact with the filter. In this latter embodiment, a potential may be applied to the filter.

In one embodiment, the method further comprises regenerating the filter by washing with an aqueous solution. In one embodiment, the fluid is a hydrocarbon oil feedstock. In some embodiments, the viscosity is reduced. In some embodiments, turbulence is increased.

[0011] The present invention also provides a method of treating an emulsion by contacting the emulsion with an adsorbent in which one phase is an electrolyte and having a surface crystal structure. The adsorbent is preferably an intermetallic compound. In some embodiments, the emulsifier is a surfactant.

The surfactant is preferably of a type having an action of inverting micelles so that the absorbent species faces outward. Preferably, the surfactant contains calcium. Preferably, the surfactant contains sodium. In one embodiment, the surfactant is of the type wherein the hydrophobic groups are long-chain and the hydrophilic groups are carboxylate.

In some embodiments, electrical energy is applied to the sorbent and the emulsion. The energy is applied as a magnetic field around the adsorbent. The energy can be applied as a DC voltage applied to the adsorbent. The applied voltage can range from 0.8V to 2.0V.

According to another aspect of the invention, one phase is the electrolyte and the emulsifier is a surfactant having the effect of inverting the micelles such that the functional group containing the heterocycle faces outward. A method for treating a liquid is provided, the method including a step of forming an emulsion and a step of contacting the emulsion with the adsorbent.

It is preferable that the adsorbent has a crystal structure. In one embodiment, the adsorbent has a defect site on a surface adjacent to the electron-deficient atom.

The present invention also provides a method for desulfurizing a hydrocarbon feed stream comprising contacting a hydrocarbon feed stream with an adsorbent having a surface crystal structure until sulfur species are adsorbed on the adsorbent surface.

It is preferable that the adsorbent has a defect site on a surface adjacent to the electron-deficient atom. In one embodiment, the sorbent is an intermetallic compound. In another embodiment, the absorbent is a SbSn intermetallic.

The present invention also provides a filter having a surface crystal structure that facilitates the adsorption of undesired chemical species onto the filter when the fluid containing the adsorbate contacts. In one embodiment, the adsorbent has a defect site on a surface adjacent to an electron-deficient atom. The adsorbent is preferably an intermetallic compound. In another embodiment, the intermetallic compound is a SnSb intermetallic compound. Preferably, the filter has means for applying electrical energy to improve adsorption.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will be more clearly understood from the following detailed description of several embodiments, given by way of example only, with reference to the accompanying drawings, in which: FIG. The present invention filters a fluid by adsorbing the fluid onto undesired species of filter surfaces. The filtration media material has a crystal structure that is well-defined with surface cavities and defects on the nanoscale, generally between 2 nm and 100 nm.

It has been found that the fluid preferably has the following properties for good processing. (A) In the case of a liquid, it is preferably an emulsion in which one phase is an electrolyte such as water containing a small amount of ionic salts to provide ionic conductivity. (B) In the case of gas, it is preferable to contain water.

For emulsions, the emulsifier is preferably a surfactant that forms a phase containing bubbles and micelles. Common types of surfactants which have been found to be suitable are anionic, ionic and amphoteric surfactants. Preferably, in the surfactant, the hydrophobic group is a long chain (eg, a fatty acid), and the hydrophilic group is a carboxylate. Na and Ca are preferably present as salts. Such surfactants are those naturally present in petroleum resins and asphaltene fractions.

Such surfactants act to reverse micelles containing undesirable species. FIG. 1 shows an embodiment in which the asphaltenes in the crude oil are reversed. The inversion of micelles is caused by the action of membrane mimetic chemistry in which the heterocyclic-containing functional groups (S, N, O) are oriented outward from the micelles. As a result, a chemical reaction such as decomposable adsorption is facilitated.

When the fluid is a gas, it must contain water and the molecules preferably have a low molecular weight of 200 or less. One example is natural gas wherein the sulfur species is H ₂ S, R ₂ S, or RSH. They all have a low molecular weight and are volatile and can therefore be surface adsorbed.

[0024] For filtration, a liquid feedstock containing the species to be adsorbed is contacted with the filter. An electrical potential can be generated in the fluid to generate an electrokinetic potential (ie, "zeta"). In another embodiment, the potential can be generated by an externally induced electric field. This potential causes the polar adsorbed species to interact with the filter surface in an environment where the micelles are inverted by the surfactant. This effect is a type of degradable adsorption in which fluid bonds, for example, S—C bonds, are broken. The nucleophilic atom strikes an electron-deficient cavity in the filter. In the case of asphaltenes, the decomposition of the adsorbate decomposes the asphaltenes into resins or aromatic compounds. FIG. 2 exemplarily shows an example.

Referring to FIG. 2, the SnSb intermetallic compound is designated by the numeral 10. The Sb atoms form electron deficient cavities 12 on the filter surface and these attract nucleophilic polar sulfur heads 13. By this action, the long chain tail portion 14 of the fluid molecule is cut by vibration and rotational forces, thereby removing elemental sulfur from the liquid.

An example of how the SbSn filter is manufactured will be described below. In the following description, the terms used in the heading of each successive part are underlined. First, melt production is performed in which an equiatomic composition of tin and antimony is melted in a graphite crucible using an induction heating furnace. Mixing of atoms is performed in this molten state. The melt is maintained at 500 ° C. for 10 minutes in a hydrogen gas cover to prevent oxidation.

The melt is poured from the bottom into an atomizing nozzle operating with high pressure nitrogen at a plenum pressure of 2.5 MPa for gas atomization . Nitrogen is exhausted through an annular gap surrounding the melt stream to form droplets. The adiabatic expansion of the gas rapidly cools the droplets and accelerates them away from the melting source. During the subsequent flight, the droplets solidify into crystal grains of the SbSn intermetallic compound with an average size of 10 μm. The particles are collected in a container containing nitrogen gas.

These particles can be used directly because their microscopic size provides a large surface area for contacting the fuel. For example, particles can be loosely packed into a column. The particles can be used by binding to a support. Further, instead of providing an integral porous structure, a support having a porous structure by coating the composition can be used. In this case, a ceramic or metal support can be used, and the composition can be coated by chemical or physical vapor deposition techniques, or by plasma spraying.

In another embodiment, the powder can be used as follows to produce a porous structure through which fuel passes for surface contact. The powder is filled following the machined graphite mold and added with about 2% stearic acid as a pore former to form a disk. The graphite is heated in a hydrogen sintering atmosphere at 370 ° C. for 30 minutes to bind the particles.

By sintering in this method, a porous filter having an optimal balance between the binding properties and the porosity is formed. The filter thus produced has the following properties: porosity 40-50% permeability 10 ^-11 m ² pore size 25 μm The following description describes another way of carrying out each step of the method according to the invention. It is shown.

Melt Preparation Method The materials used can further include other metals such as platinum, gold or palladium. The formulation need not be isoatomic. The final product, the intermetallic compound, preferably has a tin atom percentage of 39.5 to 57%. The melt can be at any temperature that does not absorb and / or react with oxygen. It will be appreciated that the material need not be melted. For example, metals can be physically combined into a single powder by mechanically alloying the separated powder with sufficient energy.

Gas atomization The atomization pressure is sufficient to provide the required high cooling rate,
Depends on the desired particle size. This is estimated to be at least 10 ³ ° C / s. For example, with a lower pressure of 0.7 MPa, a larger particle size of 20 μm can be obtained. The atomizing gas, in another embodiment, may be hydrogen, argon, helium, or any other inert gas, or any mixture of these gases.

Sintering Atmosphere The use of a hydrogen atmosphere is not essential. Due to the problems associated with using lower temperature hydrogen furnaces, the sintering behavior was studied in nitrogen and nitrogen-hydrogen atmospheres. Sintering of the filter, either in complete nitrogen or a mixture of hydrogen and nitrogen, was found to produce a black coating on the surface. This was due to the deposition of carbon on the filter surface. Stearic acid is a hydrocarbon consisting of several C—H bonds and is used as a pore-forming additive. Stearic acid combustion is facilitated by carbon-hydrogen cleavage and simple gas formation using a reducing atmosphere. Hydrogen is a reducing atmosphere and, in addition to sintering the powder, assists in burning stearic acid. The use of a nitrogen atmosphere does not cause the two processes described above due to its non-reducing behavior.

Further, the deposition of carbon on the surface hinders the sinterability of the powder. The sample sintered with the hydrogen / nitrogen combination had a black surface and was very brittle. The carbon coating was only visible on the surface, not on the other side of the filter. Also, this discoloration may be due to carbon deposition.

As an interesting phenomenon, it was recognized that carbon deposition could be prevented when the powder sample was covered with a graphite plate over the entire mold. The powder coated with the graphite plate and sintered in a nitrogen atmosphere exhibited the same sintering behavior as the powder sintered in a hydrogen atmosphere. This coated plate (made of graphite) forms carbon monoxide, a reducing atmosphere. It will be appreciated that plates other than graphite may be used if some parts of the mold are carbon when using a nitrogen atmosphere.

FIG. 3 is a partial photograph of a sample sintered in a completely hydrogen and nitrogen atmosphere. These have a similar pore structure. 100% nitrogen and 100%
Table 1 shows the permeability, density and shrinkage of the filter sintered in hydrogen.

[0037]

[Table 1]

The X-ray diffraction pattern of the sample also shows that the filters sintered using a nitrogen and hydrogen atmosphere form the same intermetallic compound phase SbSn (FIG. 4). As a result, the powder mixed with 2% by weight of stearic acid showed maximum permeability and pore size. The powder can be sintered in both a 100% hydrogen atmosphere in addition to a 100% nitrogen atmosphere, but if not in a 100% nitrogen atmosphere, the sample is covered with a graphite boat on top to reduce Give the atmosphere.
The samples sintered in a 100% nitrogen atmosphere formed the same intermetallic SbSn phase.

Sintering can be performed by heating graphite to 370 ° C. in a graphite boat configuration. In this case, oxygen reacts with graphite to form CO gas, and CO ₂ is formed by an oxidation reaction. Both reactions remove oxygen or oxides from the sintering environment. Graphite is converted to steam over time and is thus consumed continuously.

It is possible to use any suitable reducing atmosphere. Examples are methane, C
_{O, H 2, N 2 -H} 2 mixture system is the use of NH _3, and ammonolysis products.
Suitable combinations of the gases described above could be used with endothermic or exothermic combustion processes. In particular, the use of H ₂ -N ₂ is preferred since at low H ₂ levels of a few percent the atmosphere is not explosive and still has reducing properties.

Additional Step-Sintering Additive The process may include adding an additive to the intermetallic powder to provide a larger catalyst surface area to widen the pores during sintering. good. this is,
Although briefly mentioned in the above description, it will be described in more detail in this section.

In one embodiment, stearic acid was selected as a binder that was added to the powder to improve permeability. The stearic acid used is Industrene 5016 manufactured by Witco. The reason for choosing stearic acid is that it burns completely before the sintering temperature reaches 370 ° C. The stearic acid and the powder were mixed in a mixer to form a uniform blend of the powder and the binder. The total mixing time was about 2 minutes. Mixing was performed at short time intervals of 20 seconds to prevent stearic acid from melting due to heat generated in the mixer.

[0043] Sintering experiments were performed in the retort in both a nitrogen atmosphere and a hydrogen atmosphere.
Permeability experiments were performed using a permeability measurement device using air as the flow medium and mercury as the reference liquid in the column. The final density was measured using the Archimedes method. Table 2 below compares the% density and permeability of filters sintered by mixing various weight percentages of stearate with the powder at 370 ° C. in an H ₂ atmosphere.

[0044]

[Table 2]

In Table 2, all measurements are for the diameter of one filter, not for the actual filter size.
The test was performed on a powder sintered in a graphite boat cavity having a height of 9 mm and a height of 4.3 mm. Powders mixed with 2% by weight of stearic acid show a maximum permeability of 2 × 10 ^-11 m ² , approximately 50 times as high as powders mixed with 1.5% by weight and 1% by weight of binder Powders mixed at 1.5% and 2% by weight showed a decrease in density, whereas the powders showed an increase in density. Powder mixed with stearic acid showed better sintering behavior than powder not mixed with binder. The initial increase in density can be attributed to this behavior. The decrease in density in powders mixed above 1% by weight was due to excess pores formed by stearic acid combustion. The powder mixed with 2% by weight of stearic acid and sintered had a maximum pore size of 52 μm and the highest porosity. FIG. 5 shows an optical micrograph of the surface of a filter sintered from powders of 0% by weight and 2% by weight of stearic acid.

In general, any suitable agent that occupies space during heating but burns during sintering can be used. It is preferable to burn cleanly at a relatively low temperature. It has been found that powdered stearic acid is preferable at a particle size of 100 μm or less. This powder can be added while vibrating the intermetallic compound powder to allow for a lower packing density, resulting in a bulky structure with higher permeability after sintering.

All suitable pore formers having the general properties described above can be used, such as ammonium carbonate, camphor, naphtha, ice, monostearate, as well as low molecular weight waxes and organogels. Further, a pore-forming agent having an action of providing a reducing atmosphere can be used, and examples thereof include a paraffin wax that forms methane during combustion.

Also, the filter can be formed from one layer or multiple layers so that the layers can be used as “standard components” to achieve desired properties. This filter has different physical properties than the filters described above. Preferred parameter value ranges are shown below. Porosity: 30-50% Permeability: 1-400 × 10 ^-13 m ² Pore size: 3-300 μm What has been described above is one method for producing SbSn intermetallic compounds. However, such intermetallics can be produced by other techniques, such as physical vapor deposition. This depends on the structure of the filter, which in turn depends on the specific operating conditions and the type of feed stream to be processed.

[0049] SbSn intermetallics have been found to be particularly effective. Also, another metal having a similar crystal structure is expected to be effective. For example, CuZn and CuZr have close proximitys where the lattice parameters match and belong to the same Pearson space group.

Operation of Filters Regardless of their physical configuration, filters are used to treat fluids by contacting them with fluids and to absorb undesirable chemical species to the surface. The filter acts as an adsorbent, and the species in the fluid that is removed is the adsorbent. Adsorption depends on the nature of the fluid being treated and the filtration process used. Many different fluids can be processed, including many polymeric and hydrocarbon fluids.

[0051] The filtration process can be enhanced by using a magnetic field in the fluid. Alternatively or additionally, a potential can be applied to the filter itself. With such electric and / or magnetic fields, a suction gradient to the filter is obtained. Also, such an electrolysis or magnetic field allows for the selection of the species to be adsorbed.

[0052] In addition to the removal of unwanted species, filtering provides a beneficial effect on some fluids. One such effect is a reduction in the viscosity of a fluid, such as a non-Newtonian fluid containing crude oil or condensate. Another effect is a very rapid destabilization of the emulsion by reaction with a surfactant. This effect is particularly effective when the emulsifier is a surfactant containing Na and / or Ca ions. When water is introduced into the fluid to improve the filtration effect, the artificial surfactant is Na and / or
Or it is necessary to contain Ca ion. A further effect is improved turbulence.

When the filter is no longer valid, it is replaced with a clean filter and the original filter is cleaned. Cleaning is performed by applying an electric field to the filter, and if possible, cleaning with a strong alkaline cleaning fluid. However, in some cases, the filter may be cleaned with only a wash.

For the SbSn intermetallic compound filter, more specifically, a cyclic voltammogram test performed using tin-only, antimony-only, and intermetallic (IM) electrodes showed that the action of the intermetallic was simply tin. And the individual effects of antimony. These tests also show that one or more reactions occur as the voltage changes. This indicates that the filter function can be selectively adjusted when a voltage is applied.

Referring to FIG. 6, a diagram of a cyclic voltammogram is shown for an intermetallic compound filter in an equal mixture of crude oil / water. Scanning speed is 10m
V / s, but this parameter is less important as the response was found to be independent of scan speed. As is clear from these figures, c. -1.
There is a peak at 2-1.3V. This indicates that certain reactions, including species adsorption on the filter, occur at certain voltage biases. It also shows that the process is not reversible due to the absence of activity at forward bias. The next series of tests performed on the water portion of the above mixture is illustrated by FIG. Again c. There is a reaction peak at -1.2 to -1.3 V, but also two other less pronounced reaction peaks, including one at forward bias. This indicates that the reaction is irreversible and therefore requires solvent washing for filter washing. Also,
These indicate that the presence of water is important and that the active adsorbent is preferably water-soluble, such as an inorganic salt. The latter conclusion was made on the oil portion only and came from another test which showed a significant reduction in response.

The examples described below show a filtration method. Tests were performed to analyze the effectiveness of the filter in various adsorption fluids. These tests were also performed on another material-stainless steel filter.

Testing on Fuel Oils The present invention proves to be particularly useful for treating fuels such as oil and natural gas, as these have significant environmental impact. An undesirable component in such fluids is sulfur, which is usually present in the range of 100 to 1000 ppm. Sulfur not only pollutes the atmosphere itself, but also pollutes conventional catalysts for cleaning exhaust gases. Sulfur also damages engine components, such as turbine blades, and presents major design and maintenance problems, for example, in the avionics field. Sulfur is, for example, thiophene, benzothiophene,
Or in a different form, such as dibenzothiophene.

In existing technologies, hydrotreating processes are used for sulfur removal, which are effective in reducing to below 50 ppm. These processes, high temperature to remove the H ₂ S in hydrogen, is based on the high-pressure process. Recovered stream of have your refinery H ₂ S is thereafter further processed by removal and recovery of the elemental sulfur is carried out. However, these processes require not only very expensive and complex plants and control methods, but also high energy inputs, which also have a negative impact on the environment. Also, these processes will reduce some of the unsaturated organic compounds present and consume more hydrogen than is necessary to process the sulfur.

Various tests were carried out to show the beneficial effects of the oil filtration according to the present invention. The test pumped oil in a dynamic rig through a housing containing SbSn intermetallics to give a contact time of 1-5 seconds. Another test was a static one that introduced the filter into the oil in powder form.

For crude oils, the effect is de-emulsification by removal of the natural surfactant. This effect depends on the stability of the emulsion and / or the total energy input to the emulsion. The following improvements were observed: (I) Substantially high levels of inorganic sulfur species have been removed from the aqueous phase. (Ii) The pH value of water was significantly improved. (Iii) SARA analysis showed reduced asphaltene and resin components and increased aromatic components. (Iv) In the oil phase, the viscosity was significantly reduced.

It was found that when a magnetic field was applied to the liquid emulsion, the separation was delayed.
In this case, high levels of organic S were removed, and selection of the adsorbed species was achieved by adjusting the magnetic field. Similar effects were observed when a potential was applied to the filter.

Referring to FIG. 8, an experimental apparatus 10 is shown. The apparatus has a feed flask 11 in which the feedstock is sucked by a pump 12 through a powder bed 13 containing the SbSn intermetallic compound. Valve 14 allows the feedstock to be directed to either (a) a single pass stream to sampling bottle 15 or (b) a recirculating stream. The power supply 16 that supplies power to the coil 17 is
When activated, an induced magnetic field is generated in the powder bed 13. Tests were performed on crude oils having the sulfur concentrations listed in Table 3 below as determined by GC spectra.

[0063]

[Table 3]

In the first stage, the crude was pumped in the circulation for 30 minutes. The sample size was 600 ml and the volume was 2 parts water to 3 parts oil. Flow velocity 2
The amount was 0 to 25 ml / min, and the amount of the SnSb intermetallic compound powder was 40% by weight of the sample feedstock.

In the second stage, a voltage of 1.2 V was applied to generate a magnetic field, and the emulsified fluid (about 300 ml) from the first stage was transferred to a powder bed (40% of the sample weight). (Adjusted to remain) in a single pass to sampling bottle 15. The voltage level should be in the range 0.8V to 2.0V, preferably about 1.2V.

For sampling after both stages, the fluid was de-emulsified and the sample was subjected to a modified Eshka method (ASTM 3) to determine total sulfur.
177-89) and analyzed by thin layer chromatography (TLC) for SARA analysis. The results for total sulfur removal are shown below.

[0067]

[Table 4]

Table 5 below shows the SARA analysis.

[0069]

[Table 5]

Note: (a) The number to the left of / is the original and the right is the% change. (B) The number to the left of / is the% of the sample for the first stage, and the number on the right is%
It is a change. (C) Numbers in parentheses are total percent change relative to original sample.

These results indicate that the crude oil composition was changed by the intermetallic compound. With reference to the SARA composition, the objects have increased saturation and aromatics and reduced resin and asphaltenes. This benefits the downstream process in the refinery. This result indicates that the resin and asphaltenes are significantly reduced when the sequence is changed so that the applied voltage is applied first and then the operation is repeated without a voltage.

With respect to elemental sulfur, 11 organic species were identified. Desulfurization by the filter occurred uniformly over various types regardless of the presence or absence of the applied voltage. Level is 6
Reached 7.6%. By incorporating multiple filter units and increasing the surface area of the intermetallics, the level of sulfur removal would exceed the results achieved in these experiments.

The following tests were conducted on the crude oils shown in Table 3. A For the first stage described above, a flow rate of 20-25 m in the recirculation circuit
Continuous flow at 1 / min and without applied voltage B Continuous flow at a flow rate of 20-25 ml / min without recirculation and with applied voltage. This is similar to the second stage described above, except that the sample is brand new and not fluid from test A.

The SARA analysis will be described. (I) Test Type A-Asphaltene content reduced by 27%, resin content reduced by 39%, aromatic content increased by 40%, saturates content decreased slightly. (Ii) Test Type B-Asphaltene content increased by 18%, resin content increased by 8%, aromatic content decreased by 20%, saturate content increased by 6%.

Another test was performed on the crude listed in Table 3 using the apparatus 10. The total S content of the emulsified sample before and after the reaction was measured in the oil phase separated from the sample re-emulsified by the modified Eshka method and in the aqueous phase by titration and turbidimetry. These methods were used for analysis of the separated phase after the treatment. The results are shown below.

[0076]

[Table 6]

[0077]

[Table 7]

Test Using Model Solution A test was conducted using a Sb / Sn intermetallic compound filter as a powder in 40 ml of distilled water having a fixed concentration of sodium sulfide (Na ₂ S) of 348 mg-S / l. Was. For different concentrations of intermetallic compounds, the contact time was fixed at 30 hours and the adsorption was measured. Distilled water was degassed for 3 hours to avoid the effect of dissolved oxygen. The pH was controlled at 3 ± 0.5. The results are shown in FIG. 9 and it can be seen that the inorganic sulfur concentration was reduced by about 11% for 5 g of the intermetallic compound.

Thereafter, the test was carried out at different initial concentrations of Na ₂ S, a fixed contact time of 30 hours, the amount of fixed intermetallic compound (15% w / w) and a pH controlled at 3 ± 0.5. Was done. The deionized water was also degassed for 3 hours. The results are shown in FIGS. FIG. 10 shows that as the sulfide concentration increases, the ability to adsorb intermetallic compounds increases. FIG. 11 shows that the adsorption behavior of inorganic sulfides can be well explained using the Freundlich equation.

Other tests performed both with and without HCl in solution showed higher sulfur adsorption efficiencies when using HCl. This indicates that Na can be selectively adsorbed prior to S, and that the adsorption is performed better in an acidic solution (pH = 3.0).

In another test, the fluid used was dibenzothiophene (40% by volume) emulsified in distilled water by the addition of a surfactant (Span 20). The results are shown below.

[0082]

[Table 8]

These results indicate that dibenzothiophene is particularly difficult to remove,
It is very important.

Testing on Partially Refined Fuels A partially purified oil, naphtha, was also tested where the major S-containing compounds were substituted thiophenes, benzothiophenes and a small percentage of dibenzothiophenes. . This test was performed on a polymer coated with Sb / Sn intermetallic compound.
It was dynamic, pumping oil through the housing containing the Raschig ring.

The presence of water is necessary to obtain a significant sulfur reduction that gives optimal results when the whole naphtha is emulsified with water and filtered. Washing with water prior to treatment resulted in a 10% to 30% reduction. Complete emulsification of naphtha with water with added surfactant improved the properties. Tested 1700
It was shown that sulfur was reduced from ppm to 700 ppm.

[0086] Tests on diesel fuel have shown that sulfur levels are reduced by 40% without water treatment. Gasoline showed a significant improvement without water treatment. In these tests, a possible approach to filtration is in several stages, in which the crude oil arriving at the refinery is first processed, the intermediate treatment during the refining process (naphtha) and finally the final This indicates that the processing of the final stage of the product is performed.

It is known that the organic sulfur species in lighter petroleum (gasoline, diesel and naphtha) is different from heavy petroleum (crude and heavy oils with high sulfur content). Lighter petroleum mostly contains polar or polarizable sulfur compounds such as mercaptans and hydrogen sulfide, while heavy oils contain polarizable sulfur compounds such as dibenzothiophene. They remove polar or polarizable sulfide compounds more effectively from petroleum products than from crude petroleum.

In the naphtha test, the presence of water often results in the effective removal of either natural or artificial surfactants for intermetallic compounds and the emulsification of the two liquids. It was observed to be completely separate or essential to effectively remove sulfur species other than crude oil.

In addition, the water portion of the natural emulsion has been shown to be the active ingredient in the reaction. Furthermore, these reactions are likely to appear at specific voltages and current densities. By reproducing these conditions, it was shown that by precisely adjusting the voltage, specific elements could be removed from the crude oil without affecting the emulsion state of the liquid.

Regeneration of Filters For commercial applications of the invention, it is important that the filters can be repeatedly washed for reuse. The filter system removes the filter from the flow conduit and
It consists of a control system for cleaning the filter and then returning it to the flow conduit.

The surface of the filter was found to be cleaned by immersion in a cleaning solution and application of voltage. In one embodiment, the cyclic voltammogram is
1.5Vvs. SCE and 1.5Vvs. Performed in the SCE range. The cleaning liquid is water,
Alconox detergent and water again. The current levels were observed to return to the same range as for the first water test, indicating that the detergent removed a significant amount of sulfur. XPS analysis of one filter showed that 6 atomic% S was reduced to near zero.

Filtration of Another Fluid The filtration method of the present invention can be used for other fluids. For example, gases such as natural gas, combustion products, or polluting gases can be treated. In some embodiments, blood can be processed to remove unwanted polar molecules. More generally, food or medical products can be processed to remove unwanted components. Further, polluted wastewater and seawater can be effectively treated.

[Brief description of the drawings]

FIG. 1 is a diagram showing inversion of asphaltene micelles in a fluid to be adsorbed.

FIG. 2 is a diagram showing adsorption of sulfur.

FIG. 3 is a scanning electron micrograph of a sample of an SbSn filter sintered in a 100% hydrogen atmosphere.

FIG. 4 is an X-ray diffraction pattern of a sintered SbSn powder.

FIG. 5 is an optical micrograph of the surface of an SbSn filter.

FIG. 6 is a diagram showing a cyclic voltammogram showing a reaction of a fluid with a filter.

FIG. 7 is a diagram showing a cyclic voltammogram showing a reaction of a fluid with a filter.

FIG. 8 shows an experimental configuration for the treatment of a hydrocarbon liquid.

FIG. 9 is a diagram showing the adsorption of inorganic sulfur on an intermetallic compound filter.

FIG. 10 is a diagram showing the adsorption of inorganic sulfur on an intermetallic compound filter.

FIG. 11 is a diagram showing the adsorption of inorganic sulfur on an intermetallic compound filter.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, GM, HR, HU, ID, IL, IS, JP, KE, KG, KP , KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW Vermont Avenue 3620, Caprilian Hall 224A, University of Southern Calif. (72) Inventor Iacocca, Ronald United States, Pennsylvania 16803, State College, Belmont Circle 649 F-term ( 4D017 AA04 BA11 CA04 CB01 CB05 DA01 DB01 DB04 EB08 EB10 4G066 AA02B AA04D BA31 CA22 DA04 DA07 DA09 FA22 FA40 GA11

Claims (39)

[Claims] 1. A method for treating a fluid containing an undesired species, comprising contacting the fluid with a filter having a surface crystal structure, and adsorbing the undesired species of the fluid onto the filter. A method comprising the step of facilitating. 2. The method of claim 1, wherein the filter has defect sites on a surface adjacent to electron-deficient atoms. 3. The filter according to claim 1, wherein the filter is made of an intermetallic compound.
Or the method of 2. 4. The method according to claim 3, wherein the metals of the intermetallic compound are Sb and Sn. 5. The method according to claim 1, wherein the fluid contains water. 6. The method of claim 5, wherein said fluid is a liquid and is an emulsion. 7. The method of claim 6, wherein one of the emulsion phases is an electrolyte.
The method described in. 8. The method according to claim 7, wherein the emulsifier is a surfactant. 9. The surfactant is of a type having a function of inverting micelles containing a group containing a heterocyclic ring such that the groups are oriented outward. 9. The method of claim 8, wherein the method comprises: 10. The method according to claim 9, wherein the surfactant is of a type wherein the hydrophobic group has a long chain and the hydrophilic group is carboxylate. 11. The method according to claim 1, wherein a magnetic field is applied to the fluid so that the fluid contacts the filter. 12. The filter according to claim 1, wherein a potential is applied to said filter.
A method according to any one of the preceding claims. 13. The method according to claim 1, further comprising the step of regenerating the filter by washing the filter with an aqueous solution. 14. The method according to claim 1, wherein the fluid is a hydrocarbon oil feedstock. 15. The method according to claim 14, wherein the viscosity is reduced. 16. The method according to claim 14, wherein turbulence is increased. 17. A method for treating an emulsion in which one phase is an electrolyte, the method comprising contacting the emulsion with an adsorbent having a surface crystal structure. 18. The method according to claim 17, wherein the adsorbent is an intermetallic compound.
The method described in. 19. The method according to claim 17, wherein the emulsifier is a surfactant. 20. The method of claim 19, wherein the surfactant has the effect of inverting micelles so that the adsorbed species faces outward. 21. The method according to claim 20, wherein said surfactant comprises calcium. 22. The method according to claim 20, wherein the surfactant contains sodium. 23. The method according to claim 20, wherein the surfactant is of a type wherein the hydrophobic group has a long chain and the hydrophilic group is carboxylate. . 24. The method according to claim 17, wherein electric energy is applied to the adsorbent and the emulsion. 25. The method of claim 24, wherein the energy is applied as a magnetic field around the sorbent. 26. The method of claim 24, wherein the energy is applied as a DC voltage applied to the sorbent. 27. The method according to claim 26, wherein the applied voltage ranges from 0.8V to 2.0V. 28. A process for forming an emulsion, wherein one phase is an electrolyte and the emulsifier is a surfactant having a function of inverting micelles so as to orient a heterocyclic-containing functional group outward. Contacting the emulsion with an adsorbent. 29. The method of claim 28, wherein said sorbent has a crystalline structure. 30. The method of claim 29, wherein said adsorbent has defect sites on a surface adjacent to its electron deficient atoms. 31. A process for desulfurizing a hydrocarbon feed stream, comprising contacting a feed stream with an adsorbent having a surface crystal structure until sulfur species are adsorbed on the adsorbent surface. 32. The method of claim 31, wherein said adsorbent has defect sites on a surface adjacent to its electron deficient atoms. 33. The method according to claim 32, wherein the adsorbent is an intermetallic compound.
The method described in. 34. The method according to claim 33, wherein the adsorbent is an SbSn intermetallic compound. 35. A fluid filter comprising an adsorbent having a surface crystal structure that facilitates the adsorption of undesired species to the filter when the fluid containing the adsorbate contacts the fluid filter. 36. The filter according to claim 35, wherein the adsorbent has a defect site on a surface adjacent to an electron-deficient atom. 37. The method according to claim 35, wherein the adsorbent is an intermetallic compound.
Or the filter of 36. 38. The filter according to claim 37, wherein the intermetallic compound is a SbSn intermetallic compound. 39. The filter according to claim 35, further comprising means for applying electric energy to improve adsorption.