CN101495434A - Method for removing sulfur compounds from an alcohol stream - Google Patents
Method for removing sulfur compounds from an alcohol stream Download PDFInfo
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- CN101495434A CN101495434A CN 200780020527 CN200780020527A CN101495434A CN 101495434 A CN101495434 A CN 101495434A CN 200780020527 CN200780020527 CN 200780020527 CN 200780020527 A CN200780020527 A CN 200780020527A CN 101495434 A CN101495434 A CN 101495434A
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Abstract
Processes, apparatus, and systems for purifying alcohol streams by reducing the concentration of sulfur compounds in those alcohol streams are presented herein. The invention is exemplified by reduction of sulfur dioxide, sulfate ion, and sulfite ion in an ethanol stream, but is applicable for the removal of other sulfur compounds from other alcohol streams.
Description
Cross-reference with related application
The application requires to enjoy the unsettled U.S. Provisional Patent Application series number of submitting on April 5th, 2,006 60/789, the unsettled U.S. Provisional Patent Application series number 60/855 that on October 27th, 470 and 2006 submitted to, 017 benefit of priority, the identical and title of its contriver is " removing the method for sulphur compound from alcohol stream ".It is for referencial use to incorporate U.S. Provisional Patent Application series number 60/789,470 and 60/855,017 into this paper, just as in full openly in this application.
Background of invention
1. invention field
Ethanol extensively is used for the synthetic of coating, medicine and intermediate, makeup, spices and other products as solvent in industry.Dehydrated alcohol (that is dewatered ethanol) also is a component important in the fuel substitute.Fuel substitute can distillate the combination results of component by ethanol and for example gasoline and other fossil oil.These fuel substitutes may comprise, for example, E10 alcohol blended fuel or E85 alcohol blended fuel (containing 10% and 85% dehydrated alcohol respectively), the alcoholic acid percentage composition can change according to the purposes of expection certainly.Dehydrated alcohol also can be used as important oxygenated additive in white gasoline.
Because ethanol, methyl alcohol and the complicacy of other alcohol stream in modern Application are desirable to provide this high as far as possible class alcohol stream of purity.Common a kind of impurity is sulphur in the alcohol stream.This sulphur may be with for example, sulfate anion and compound thereof, and inferior sulfate radical negatively charged ion and compound thereof, perhaps the form of sulfurous gas exists.Those of skill in the art will recognize that in alcohol stream and also may have other sulphur compound.
The reason that sulphur compound may exist in ethanol stream is a lot.For example, originally they may be present in the bed blending that is used for producing ethanol stream/or because introducing of sulphur compound in obtaining the alcoholic acid course of processing.May comprise by the ethanol stream of wet milling process, for example, be the sulphur of sulfurous gas form at least about 8ppm (that is about 8mg/L) from Maize Production.May comprise by the ethanol stream of dry grinding method, for example, be the sulphur of sulfurous gas form at least about 2ppm from Maize Production.
So be desirable to provide the method, apparatus and system that reduce the sulphur compound in ethanol, methyl alcohol and other alcohol stream.
The invention summary
This paper has described by reducing sulfur compound concentration in those alcohol streams purify novel method, device and the system of alcohol stream.Enumerated the present invention by the sulfurous gas, sulfate ion and/or the sulfite ion that reduce in the ethanol, but the present invention is applicable to also from other pure stream and removes other sulphur compound.In one embodiment, the short-chain alcohol streams of having purified.
An embodiment comprises the method that removes at least a sulphur compound from alcohol.This method can comprise: a certain amount of alcohol that contains at least a sulphur compound is contacted: anionite-exchange resin, aluminum silicate clay, hydrated aluminium silicate (aluminum oxide), gac, terre verte, barium salt and their mixture with at least a material that is selected from down group; Wait for that time enough makes described material the amount of sulphur compound can be reduced to predetermined amount, and reclaim alcohol, it comprises the sulphur compound that at least a content is not more than described predetermined amount.
In another embodiment, the present invention includes the alcoholic acid system that has reduced sulphur that produces.This system can comprise: crop-processing equipment, and this equipment is set to, and sulfocompound is added in the cereal materials stream, and/or forms the cereal materials stream that contains at least a sulfocompound inherently; The fermented grain device, this device is set to, from the feedstream fermenting alcohol of sulfur-bearing and form fermented liquid; Enriching apparatus, this device is set to, and from the ethanol cut of fermented liquid acquisition enrichment, wherein, the ethanol cut of described enrichment contains the sulfocompound of 4ppm at least; And desulfurizer, this device is set to, and removes at least a portion sulfocompound from the ethanol cut of enrichment, wherein, is provided with the device that is used for removing at least a portion sulfocompound from the ethanol of enrichment in the described sweetener.This removes step and can finish by disclosed other method among the application.
In another embodiment, be provided for reducing the material of sulphur compound as follows: be slurry, Continuous Flow movable bed, countercurrent extractor, moving-bed, fixed bed, ion exchange system, ion exchange column, immersion filtration device or its combination automatically.
In another embodiment, the amount of sulphur compound reduce to and be lower than 4ppm, 3ppm, 2ppm, 1ppm, 0.5ppm or 0.1ppm in alcohol can being flowed.In the further embodiment of the present invention, comprise sulphur compound in the alcohol stream before handling more than 4ppm.In another embodiment of the invention, the sulphur compound that is removed is selected from sulfurous gas, sulfate anion, inferior sulfate radical negatively charged ion and composition thereof.
In yet another embodiment, the material that is used to remove sulphur compound is an aluminum silicate clay.Aluminum silicate clay for example may be, but is not limited to: polynite, wilkinite, zeolite clay or zeolites clay.Wilkinite may be calcium bentonite (calcium bentonite clay).
In yet another embodiment, the material that is used to remove sulphur compound is an ion exchange resin.In one embodiment, ion exchange resin be macropore and be the weak base anion exchanger, highly basic 1 type anionite, or highly basic 2 type anionites.Ion exchange resin can be, for example, but be not limited to: Mitsubishi WA30, MitsubishiDCA11, LewatitS4228, Lewatit S4528, Amberlyst A26, Amberlyst A21, LewatitMono+MP500, Dowex 22, Dowex 66, Mitsubishi PA412 and MitsubishiPA312.
In yet another embodiment, the material that is used to remove sulphur compound is a barium salt.This barium salt for example may be, but is not limited to: hydrated barta, barium carbonate or both mixtures.The barium salt that uses among the present invention may be than barium sulfate bigger in ethanol in the solubleness of alcohol in (for example ethanol).
The alcohols that relates in purification process of the present invention may comprise, for example, and ethanol, methyl alcohol, or its mixture.In a preferred embodiment, described alcohol is ethanol.
Another embodiment comprises and contains the ethanol that is less than about 4ppm sulphur compound.
The accompanying drawing summary
Fig. 1 illustrates the typical corn dry mill legal system that comprises desulfurization and is equipped with alcoholic acid technology, as comprising in one embodiment of the invention.
Fig. 2 illustrates the schema that typical wet milling process is produced starch.Show the place that to introduce sulphur compound.
Fig. 3 illustrates the schema of the typical ethanol production technique of the starch that uses wet milling process production.Show the place that may remove sulphur of proposition.
Detailed Description Of The Invention
Except as otherwise noted, the term among the application should have the implication that they are accepted for the art. In order to help to understand the present invention, some term definitions are as follows.
Term " terre verte " represents a kind of clay with three layer crystal body structures as used herein, that is, and and an alumina layer and two silicon dioxide layers. Terre verte is characterised in that hydration swelling and colloidal characteristics.
Term " bentonite " represents a kind of colloidal clay as used herein, mainly is comprised of montmorillonite (montmorillonte), but also comprises other terre verte. There are two kinds of forms of sodium bentonite and calcium bentonite. Sodium bentonite has high swellbility in water, and calcium bentonite does not have. Term " zeolite " expression aluminium and sodium or calcium or both hydrosilicates comprise having SiO as used herein4And AlO4The tectosilicate of interlocking tetrahedral structure. It can be natural or artificial being used for zeolite of the present invention. Zeolite can be sodalite, heulandite or chabasie. " zeolite-like materials " comprises mineral and the compound that has with structure like the zeolite facies and/or character. Zeolite-like materials comprises phosphate and silicate. Representational natural phosphate comprises kehoeite, ropy lava (pahasapaite) and hydroxyl phosphorus aluminium bromellite (tiptopite). Representational natural silicate comprises hsianghualite, beryllium silicon sodium stone (lovdarite), viseite, handkerchief water chalcomorphite (partheite), prehnite, water chalcomorphite (roggianite), fish-eye stone, gyrolite, water calcium lead ore (maricopaite), okenite, tacharanite and tobermorite.
Zeolite generally is to comprise SiO4And AlO4The interlocking tetrahedron at interior tectosilicate. Usually the ratio of (Si+Al)/O is 1/2. Silicate structure is electronegative and attract to be present in wherein electropositive cation. Different from other tectosilicate class (tectosilicates) of great majority, have large space, room or cage in the structure of zeolite, can hold large cation. These large cations may include, for example, but not limited to, and sodium, potassium, barium and calcium, and larger molecule and cation group comprise water, ammonia, carbanion and nitrate ion. In some zeolites, these spaces are interconnected and form passage length, wide (size depends on mineral structure) of different size here. These passages can make the easily described structure of turnover of resident ion and molecule. Zeolite is common to be characterised in that, they can lose and absorb moisture and do not destroy their crystal structure. Described major path is a kind of explanation for the consistent low proportion of zeolite.
Term " imvite " and " montmorillonite " expression has a following class clay that roughly forms as used herein:
[(1/2Ca，Na)
0.7(Al，Mg，Fe)
4(Si，Al)
8O
20(OH)
47nH
2O]。
As incorporate into described in this paper Hawley ' s Condensed Chemical Dictionary for referencial use (1987 the 11st edition) (Sax and Lewis edit), montmorillonite is bentonitic main component.
Term " short chain alcohol " is illustrated in the alcohol that has one to six carbon in its longest carbochain as used herein.
The instruction of this paper comprises provides the alcohol that comprises one or more sulphur compounds stream. Sulphur compound includes, for example, but not limited to, elementary sulfur, sulfur dioxide, hydrogen sulfide, sulfur trioxide and the compound and the ionic species that contain sulfate radical, inferior sulfate radical and/or sulfide. Alcohol flows preferably short-chain alcohol streams. Ethanol stream and methyl alcohol stream are particularly preferred.
Desulfurization from alcohol such as this paper enlightenment can be carried out before or after this dehydration of alcohols. Desulfurization is preferred after the dehydration.
The alcohol stream that can handle the sulfur-bearing that provides by described method herein is with the amount of the sulphur that reduces them and comprised.On the one hand, the alcohol stream with sulfur-bearing contacts for some time with ion exchange resin.Ion exchange resin can be for example, but to be not limited to macropore and weak base anion exchanger, highly basic 1 type anionite or highly basic 2 type anionites.Gel type resin is not too preferred.Being used for exemplary resin of the present invention comprises, for example, but be not limited to Mitsubishi WA30, Mitsubishi DCA11, Lewatit S4228, Lewatit S4528, Amberlyst A26 (Rohm and Haas), Amberlyst A21 (Rohm and Haas), Lewatit Mono+MP500, Dowex 22 (Dow Chemical Company), Dowex 66 (Dow ChemicalCompany), Mitsubishi PA412 and Mitsubishi PA312.
Those of skill in the art will recognize that gel resin generally includes the more thick pearl of low cross-linkingization, they have high capacity and high failing load.Other people recognize the gel type resin that does not have permanent pore structure.The hole that it has been generally acknowledged that them is very little, generally is not more than 30 dusts, and is called as gel pore or molecule hole.These pore structures are by the distance decision between polymer chain and the cross-linking set, and change with the crosslinking degree of polymkeric substance, polarity of solvent and with operational condition that resin adopts.Gel type resin is normally translucent.
Those skilled in the art will appreciate that also the capacity of macroporous resin is lower than the gel resin usually, but have higher anti-fouling tendency and impermeabilisation gouging abrasion more.Macroporous resin is made up of two external phases, that is, continuously the hole mutually and continuous gelatin polymer mutually.The bead micro-gel particles that described polymer phase usually structurally forms by reuniting bunch together constitutes.These bunches are anchoring at together again at the interface, form the hole that is connected with each other.The surface-area that increases derives from the surface of the exposure of microgel, and gluing forms bunch together.Macroreticular ion exchange resin can adopt different surface-area preparations.These surface-area can be for example, 7 to about 1500m
2In the scope between the/g, mean pore size from about 50 to the scope of about 1,000,000 dust.
In case with after, can be with the resin regeneration of using according to mode described herein.For example, can wash by sodium hydroxide and alcohol and regenerate.Although may comprise the resin that is in the multiple structure described herein any, the operation in a plurality of ion exchange columns is preferred.
Purification by ion exchange resin can be carried out under " room temperature " (that is, about 21-23 ℃) for example, and but, what those skilled in the art can understand is, ion-exchange can be carried out under the temperature of wide region and pressure.What those skilled in the art can also figure out is that ion-exchange can be implemented in each step in ethanol.These steps will comprise: after distillation (～90-95% ethanol) immediately, and after dehydration (99+% ethanol) immediately, or behind the nitrogen stripping, or other auxiliary purification step.The possible pH value that is used for exchange operations as herein described from about 1 to about 10 scope.The preferred pH scope that is used for exchange operations as herein described is between about 8 and 9, although also be effective less than 8 pH value.
On the other hand, desulfurization is implemented with the mixture of aluminum oxide (alumina), silica, oxidation sial, terre verte, montmorillonite, wilkinite, zeolite, zeolite-like materials, gac or its mixture by the alcohol stream of sulfur-bearing.On the one hand, the alcohol stream with sulfocompound mixes for some time filtration then in slurry with one of aforementioned substances.
Though the applicant does not wish to be bound by theory, think in the alcohol stream sulphur compound or adsorbed by described material or hold back by ion-exchange.After the amount with sulphur compound of being enough to is reduced to the time of desired level, mixture is filtered, so remove purer pure filtrate.
The advantage that present disclosure has been arranged those of skill in the art will recognize that it is crucial that temperature may not be certain as long as temperature is not extreme for this reaction, but the temperature that is higher than room temperature is preferred.
Can determine to be fit to remove the amount of resin of the vitriol (or other sulphur compound) of desired amount from pure stream.For example, can determine the equivalent of vitriol in the given ethanol stream/liter, based on the umber of vitriol in every liter of logistics.Can determine amount by following formula by the alcohol of the plastic resin treatment of given volume:
Volume
Resin* operate exchange capacity
Resin/ (the anionic equivalent of sulphur/pure volume)
Usually determine and inform the total ion exchange capacity of resin by the manufacturer.Operation capacity be resin with bonded ionic amount, at this moment, the product of plastic resin treatment is acceptable.Operation capacity is determined by experiment according to the purposes of expection by the user usually.Those skilled in the art can determine operation capacity and recognize that system design and operational condition influence operation capacity.Total loading capacity is not often mated with operation capacity, still, can utilize total volume to estimate the amount of the accessible material of resin.
For example, the ethanol stream with 11.8ppm vitriol contains the vitriol of 0.00025eq/L.(this calculating hypothesis vitriol is the unique sulphur negatively charged ion that exists.If also there is other sulphur, eq/L will be bigger).Weak basic anion exchange resin Lewatit S4228 has 1.8 to 1.9eq/L rated capacity, and 1 liter of resin of its expression can be handled the ethanol of 7600L at the most.Highly basic 2 type anionite-exchange resin Dowex 22 have the rated capacity of 1.2eq/L, and treatment capacity is a 4800L ethanol.Highly basic 1 type anionite-exchange resin PA316 from Itochu has the rated capacity of 1.3eq/L, and causing the potential treatment capacity is 5200L ethanol.If the operation capacity of known every kind of resin just can be calculated value more accurately.
The ion exchange resin operation generally includes at least two kinds of operating method, that is, and and load (work) circulation and reprocessing cycle.As about working cycle of the present invention, relate to post and handle feed ethanol and remove the time of sulphur compound from it.To contain fully aspect this in the other parts of presents.
After the working cycle, resin just should be regenerated for reusing with having crossed.For example can regenerate by aqueous NaOH, yellow soda ash, potassium hydroxide or other compound.
But, when in alcohols or oil matrix, using resin, preferably, in system, do not introduce water.Sodium hydroxide, ammonium hydroxide and other compound that regeneration in these situations can be used different concns in the ethanol/water mixture carry out, and ethanol is for example 0: 100,50: 50,90: 10,99+ than the ratio of water in the described mixture: 1.Preferred regenerative compositions for example may have, 5% in the ethanol/water mixture (by volume) sodium hydroxide solution, and ethanol is 0.5: 99.5 than the ratio of water in the described mixture.
The application of the aqueous regeneration scheme of lecturing as this paper may comprise for four steps, though the technician of ion-exchange field will recognize, can add, modify or delete some step: the 1) removing of product ethanol (moisture), in corn sweetener industry, be called as " leaching (sweeten off) " step, 2) Shi Ji regeneration step, 3) regeneration rinse step, and the 4) removing of rinse water (containing feed ethanol) is called as " water becomes syrup (sweeten on) " step.
But the described leaching step application examples water of 1 to 3 bed volume (BV) according to appointment but if necessary, can be used more or less water removing product ethanol.In one embodiment, the water of about 2BV is used to make the post effluent liquid from about 99% ethanol to being less than about 5% ethanol.The cycle rate of water also can change, and longer cycle rate causes removing more post effluent liquid usually.In one embodiment, cycle rate is between about 1 to about 5BV/ hour, and about 3 to about 4BV/ hours is preferred.Those skilled in the art will recognize that for example, lower water percentage composition causes lower regeneration efficiency in the leaching step.For example, the solution of about 90% water may cause about 70% efficient.
The amount that is used for the aqueous regeneration material of regeneration step also can change.For example, can use about 2BV to the amount between about 7BV, 5BV is preferred.In one embodiment, aqueous regeneration material is 5% sodium hydroxide solution.Those skilled in the art will recognize that, can change flow rate.Flow rate between about 3 to about 6BV/ hours is preferred, and about 5BV/ hour is particularly preferred.Also can use other alkali that is dissolved in water-based or the organic solvent.
Described regeneration rinse step is preferably carried out under enough flow velocitys to remove the regeneration reagent in the post bed; This flow velocity becomes according to reagent.But described water becomes syrup step application examples as, the feed ethanol between about 1BV and the about 6BV, and wherein, the ethanol of feed ethanol and water ratio are between about 90: 10 to about 99.5: 0.5.Flow rate can change between about 3BV/ hour to about 6BV/ hour.The feed ethanol (99+%) that preferred amount comprises 2.7BV is to obtain under the 3.6BV/HR from 0% ethanol to 99+% alcoholic acid effluent.Then resin is put back to working order and reuse.What those of ordinary skill can be understanded is that these conditions are in no case represented the restriction to this paper embodiment scope.Those skilled in the art can use other condition.
In another aspect of the invention, remove sulphur compound by carrying out with barium sulfate form precipitated sulfur compound from pure stream.This can be undertaken by the alcohol stream of handling sulfur-bearing with barium compound.Suitable barium compound for example comprises, but is not limited to hydrated barta and barium carbonate.Can use the compound that comprises other II family element and precipitate, they cause the formation of in alcohols, particularly ethanol very little solubleness or undissolved sulphur compound.The suitable compound that comprises II family element may comprise strontium or radium.For example, the oxyhydroxide of strontium or radium and carbonate may be applicable to the present invention.
Can alcohol stream be mixed for some time with hydrated barta and remove sulphur compound from alcohol stream in slurry by for example.Because barium sulfate is insoluble to or the atomic alcohol that is dissolved in, so barium sulfate will precipitate from mixture.Mixture can be filtered, can collect the pure filtrate that purifying is crossed.On the one hand, utilize continuous filter, perhaps by obtaining mixture and filtrate simultaneously with the impregnated strainer of barium compound.
In another aspect of the invention, from alcohol stream, remove sulphur compound with one or more metallic contact by the alcohol stream that will contain one or more sulphur compounds.The metallic surface can remove vitriol and can be oxidized to other sulphur compound of vitriol.Applicable metal includes, but not limited to iron, copper or zinc.Contact between metal and the alcohol stream can realize by pure metal, metal alloy or its combination being added in the alcohol stream.By filtration, evaporation or another kind of method well known by persons skilled in the art metal is separated with alcohol then.In another embodiment, allow pure stream flow through the bed of metallic particles or metal wool.
The same with other embodiment of the present invention, can use this embodiment and satisfy maximum sulfate technical requirements in the fuel alcohol.It also can be used for satisfying restriction can be the technical requirements of the sulphur compound of vitriol by oxidation conversion; May be for example, superoxide transforms that this thing happens in the vitriol test.
Utilize metallic contact and from alcohol stream, remove sulphur compound and can combine (side by side or one after the other) use with described other method herein.For example, metallic contact can be used in combination with the ion exchange resin that is used for reducing vitriol.In this operation, under the situation of metal ion lixiviate, can use any method well known by persons skilled in the art and remove them.For example, can use the metal that Zeo-karb or resin remove lixiviate.
In another embodiment of the present invention, the metal that is used to remove sulphur compound is attached at matrix, includes but not limited to nonmetal basal body or ion exchange resin.Those skilled in the art will recognize that,, can use this method for multiple metal with to multiple alcohol stream with the enlightenment of this paper.
With advantage of the present disclosure, can determine easily that the sulphur of realizing expection in the method as herein described reduces the required time.Usually, the longer treatment time causes the more substantial of sulphur compound to remove, although reach the point that reduces the repayment of time of dropping into the most at last.
Though may being applicable to, method as herein described handles the alcohol stream have any initial sulphur load, but in embodiment preferred of the present invention, pure stream to be processed comprises at least 1ppm sulphur compound, 2ppm sulphur compound, 3ppm sulphur compound, 4ppm sulphur compound, 5ppm sulphur compound, 6ppm sulphur compound, 7ppm sulphur compound, 8ppm sulphur compound, 9ppm sulphur compound, 10ppm sulphur compound, 11ppm sulphur compound and 12ppm sulphur compound at least at least at least at least at least at least at least at least at least at least.
Method as herein described can be decreased to the amount of sulphur compound in the alcohol stream or be lower than required level.In various embodiments of the present invention, for example, the amount of sulphur compound is decreased to no more than 4ppm, no more than 3ppm, no more than 2ppm, no more than 1ppm and no more than 0.5ppm.
May be during alcohol flows because a variety of causes comprise sulphur compound, the specific mechanism that sulphur compound is introduced into alcohol stream may have nothing to do with determining the method that removes it.For example, may in wet-milling factory or dry grinding factory from the process of corn product production ethanol stream, sulphur compound be introduced ethanol stream.The technology of milling that sulphur may be introduced ethanol stream is shown among Fig. 1 and Fig. 2.
Those skilled in the art will recognize that, exist certain methods to be used for measuring the sulphur concentration of alcohol stream.For example, people can utilize the ion chromatographic column with electrical conductivity detector to measure the concentration of sulphur.Moving phase in the post is the solution of water, methyl alcohol and sodium hydroxide usually.Other method of measuring the sulphur compound in the alcohol stream comprises ASTM method D2622-03 (" wavelength dispersion Xray fluorescence spectrometer ") and D5453-03a (" sulphur analyser ").
Method as herein described can use separately or combination is used.The combination time spent, removal methods may be (in single reaction vessel or parallel carrying out) or an order simultaneously.Can repeat as required or change and remove step to improve usefulness.
With advantage of the present disclosure, those skilled in the art will recognize that, there is the whole bag of tricks, wherein, alcohol stream can be contacted with desulfurization composition described herein.For example, can be with logistics and desulfurization composition at slurry, tempering tank, ion exchange column, moving-bed ion exchange device, counter current ion exchange device, continuous filter or fusion in the strainer of described composition dipping.Circulation may be successive or be periodical operation.If necessary, can filter by for example, the centrifugal or auxiliary sedimentation of gravity removes the exhausted sweetening substance.
Embodiment
Following embodiment has set forth all respects of the present invention in more detail.These embodiment are not in order to limit the scope of all respects of the present invention.
Embodiment 1-utilizes anionite-exchange resin desulfurization from ethanol
Finished several tests, wherein, the 0.1L ethanol sample that will comprise about 12ppm vitriol is put into beaker and the stirring at room temperature that fills 0.005L anionite-exchange resin.After about one hour, test the sulphate content of each ethanol sample.In test, realized sulphate content (by ion-chromatographic determination) less than 1ppm with macroporous resin, (for example be included in weak base anion resins, Dowex 66, can derive from Dow Chemical Company) test in and with strong base anion resins (for example, Amberlyst A26, can derive from Rohm and Haas Company, and Dowex 22, can derive from Dow Chemical Company) test in.With the test of gel type resin Amberlyst A24, sulphate content is not reduced to and is lower than 1ppm.
Embodiment 2-utilizes wilkinite and the desulfurization from ethanol of other sorbent material
Finished several tests, wherein, the 200 normal intensity alcoholic acid samples that 100ml comprised about 11.7ppm vitriol (and about 0ppm sulphite) mix in 250ml pyrex nut bottle with the 5.0g sorbent material.The water-bath that this solution is put into heating make it about 50 ℃, stir under operation one night (at least 8 hours).From water-bath, shift out solution, flow through 1 micron filter paper; Gained ethanol filtrate is carried out the ion chromatography of sulphite and sulphate content.The sorbent material that uses and the sulphite of generation and the amount of vitriol are shown in table 1.
Table 1
| Sorbent material | Sulphite content (ppm) | Sulphate content (ppm) |
| Spherical Makall (silica gel 0.5-1.5mm diameter) | Do not record | 4.6 |
| Gac (Pittsburgh) | Do not record | 1.2 |
| U.S.Silica F-55 | Do not record | 10.5 |
| Active 28 * 50 order Alumina Oxide | Do not record | 0.2 |
| Oil Dri Agsorb Ultra Clear 16/30 (wilkinite) | 0.2 | 0.6 |
Embodiment 3-utilizes barium salt desulfurization from ethanol
Will about 0.085g hydrated barta be added in the 0.250L ethanol and stir about one hour.Utilize 0.2 micron filter paper filtering mixture.Use ion chromatography analysis filtrate.Filtrate comprises the vitriol of about 1.9mg/l.
The regeneration of embodiment 4-ion exchange column
Carried out being used for regeneration from the ion exchange unit of ethanol stream desulfurization.Under 3.6BV/ hour, the water of about 2.1 bed volumes (BV) that circulate is reduced to effluent and is less than 0.5% ethanol from 99+% ethanol.5% aqueous sodium hydroxide solution of the about 5BV of circulation was regenerated down at about 5BV/ hour.Utilize the deionized water of 5BV to carry out regeneration rinse step with about 5BV/ hour speed.Carry out described water with the feed ethanol (99+% ethanol) of 2.7BV and become the syrup step, under 3.6BV/HR the drive post effluent from 0% ethanol to 99+% ethanol.Then resin being put back to working order reuses.
Embodiment 5-purifies by electrodialysis and electrodeionizationization (Electrodeionization)
In electrodialysis and electrodeionization method, utilize electrical drive power (voltage) to carry ion to pass ion-exchange membrane.Contain＞ethanolic soln of 10ppm sulfate ion is recycled and flows through electrodialysis stack.This tower is made up of a series of alternately chambers by cationic exchange membrane and anionresin film production, and described film is arranged in parallel the formation compartment.Pass described tower and apply suitable dc voltage (30-40 volt).Sulfate ions permeate moves by the anion-exchange membrane anode, obtains not containing substantially (＜0.5ppm) the retentate part of sulfate ion.Spent ion exchange resin or porousness ion-exchange sheet are filled the space between anionic membrane and the cationic membrane, carry with very low concentration to promote sulfate ion.
Embodiment 6-purifies by metallic contact
Finished a test, wherein, one of material of listing in ethanol sample and the table 2 has been contacted.Leave standstill after sample vibrated about one hour.Be used for analyzing from each sample decant part liquid.The material of test has iron powder, copper powder, steel wool and bronze wool.Consumption is per 70 milliliters of ethanol, 2 gram metals.Analysis comprises, before with hydrogen peroxide oxidation and afterwards by ion chromatography test vitriol and sulphite.Use the oxidation of hydrogen peroxide and all sulphur compounds are converted into vitriol.
Table 2
These results show that unoxidized sulfate concentration is decreased to 0.3mg/L from 1mg/L, and the vitriol after the oxidation is reduced to 1.0mg/L from 8.4mg/L.
Can test other metal that is the various combination form.Metallic particles or metal wool packed in the post and make alcohol flow through it will confirm that other vitriol reduces.Can determine fully to reduce the amount of the required metal of level of sulfocompound according to experiment.Also can utilize the physics and the chemical treatment of the saturated sorbent material that is intended to regenerate, will increase catalytic performance or absorptive character as physics and chemical treatment to the metallic surface.These conditions include, but not limited to cleaning, abrasion, conversion, thermal treatment, oxidation or reduction, acid or alkaline purification or other method.Also can use attached to the various metals on the nonmetal basal body or with ion exchange resin bonded metal ion.
Although described specific embodiments of the present invention for explaination, it is obvious to the skilled person that can do multiple variation and do not depart from that the appended claim book limits the present invention.
Claims (15)
1. remove the method for at least a sulphur compound from alcohol, it comprises:
A. the alcohol that comprises at least a sulphur compound with first amount contacts with at least a material that is selected from down group: anionite-exchange resin, aluminum silicate clay, hydrated aluminium silicate, aluminum oxide, gac, terre verte, zinc, copper, brass, iron, metal, and the metal of matrix bond, and ion exchange resin bonded metal, barium salt and composition thereof;
B. wait for that time enough makes described material the amount of described sulphur compound is reduced to the predetermined amount of described sulphur compound; And
C. reclaim the alcohol of second amount, it comprises the described at least a sulphur compound that content is not more than described predetermined amount.
2. produce the alcoholic acid system that has reduced sulphur, it comprises:
A. crop-processing equipment, this equipment is set to, and sulfocompound is added in the cereal materials stream, and/or forms the cereal materials stream that contains at least a sulfocompound inherently;
B. fermented grain device, this device is set to, from the feedstream fermenting alcohol of described sulfur-bearing and form fermented liquid;
C. enriching apparatus, this device is set to, and obtains the ethanol cut of enrichment from described fermented liquid, and wherein, the ethanol cut of described enrichment contains the sulfocompound of 4ppm at least; And
D. sweetener, this equipment is set to, from the ethanol cut of described enrichment, remove at least a portion sulfocompound, wherein, be provided with in the described sweetener and be used for from the ethanol cut of described enrichment, removing the device of described part sulfocompound by the method for claim 1.
3. the system of the method for claim 1 or claim 2, wherein, the described predetermined amount of described sulphur compound is selected from the group of being made up of 4ppm, 3ppm, 2ppm, 1ppm, 0.5ppm and 0.1ppm.
4. the system of the method for claim 1 or claim 2, wherein, the ethanol of described first amount comprises the described sulphur compound more than 4ppm.
5. claim 1 or 2 method, wherein, described sulphur compound is selected from the group of being made up of sulfurous gas, sulfate anion and inferior sulfate radical negatively charged ion.
6. the system of the method for claim 1 or claim 2, wherein, described aluminum silicate clay comprises the clay that is selected from by polynite, zeolite clay, zeolites clay and the group formed thereof.
7. the system of the method for claim 1 or claim 2, wherein, described aluminum silicate clay comprises wilkinite.
8. the system of the method for claim 1 or claim 2, wherein, described aluminum silicate clay comprises calcium bentonite.
9. the system of the method for claim 1 or claim 2, wherein, described Ion Exchange Medium is a macroporous resin, it comprises at least a in weak base anion exchanger, highly basic 1 type anionite or the highly basic 2 type anionites.
10. the system of the method for claim 1 or claim 2, wherein, described ion exchange resin is selected from the group of being made up of Mitsubishi WA30, Mitsubishi DCA11, Lewatit S4228, Lewatit S4528, Amberlyst A26, Amberlys A21, Lewatit Mono+MP500, Dowex 22, Dowex 66, Mitsubishi PA412 and Mitsubishi PA312.
11. the method for claim 1 or the system of claim 2, wherein, described barium salt is selected from least one member in the group of being made up of hydrated barta and barium carbonate.
12. the method for claim 1 or the system of claim 2, wherein, the solubleness of described barium salt in ethanol is than barium sulfate bigger in ethanol.
13. an ethanol, it comprises the sulphur compound less than about 4ppm.
14. the process of claim 1 wherein that described alcohol is selected from the group of being made up of ethanol, methyl alcohol and composition thereof.
15. the method for claim 1 or the system of claim 2, wherein, at least one member who organizes down, provide described at least a material: slurry, Continuous Flow movable bed, countercurrent extractor, moving-bed, fixed bed, automatic ion exchange system, ion exchange column and immersion filtration device.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US78947006P | 2006-04-05 | 2006-04-05 | |
| US60/789,470 | 2006-04-05 | ||
| US60/855,017 | 2006-10-27 |
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| CN101495434A true CN101495434A (en) | 2009-07-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696152B (en) * | 2009-09-30 | 2012-11-07 | 郑州大学生化工程中心 | Method and device for separating cellulosic ethanol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696152B (en) * | 2009-09-30 | 2012-11-07 | 郑州大学生化工程中心 | Method and device for separating cellulosic ethanol |
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