1. A process comprising:
a) introducing in a reactor a stream (A) comprising ethanol, optionally water, and optionally an inert component,
b) contacting said stream (A) with an acidic catalyst in said reactor at conditions effective to dehydrate at least a portion of the alcohol to make a corresponding olefin having the same number of carbon atoms as the alcohol,
c) recovering from said reactor a stream (B) comprising the olefin, water and optionally the inert component and unconverted alcohol,
d) optionally fractionating the stream (B) to recover the optional unconverted alcohol and recycling said optional unconverted alcohol to the reactor of step a),
e) optionally fractionating the stream (B) to recover the optional inert component, the water and the olefin, and optionally recycling said optional inert component and optionally a part of the water to the reactor of step a),
wherein:
f) introducing a component comprising a nitrile in stream (A) or directly in the reactor wherein the nitrile is in the amount ranging from 0.01 wppm to 10 wppm relative to the ethanol and is capable to neutralize a part of the catalyst active site; and
g) optionally the temperature of the reactor is adjusted to increase the alcohol conversion, the olefin yield, or both.
2. A process comprising:
a) introducing in a reactor a stream (A) comprising ethanol, optionally water, optionally an inert component
b) contacting said stream (A) with an acidic catalyst in said reactor at conditions effective to dehydrate at least a portion of the alcohol to make a corresponding olefin having the same number of carbon atoms as the alcohol,
c) recovering from said reactor a stream (B) comprising the olefin, water and optionally the inert component and unconverted alcohol,
d) optionally fractionating the stream (B) to recover the optional unconverted alcohol and recycling said optional unconverted alcohol to the reactor of step a),
e) optionally fractionating the stream (B) to recover the optional inert component, the water and the olefin, and optionally recycling said optional inert component and optionally a part of the water to the reactor of step a),
wherein:
f) introducing a component comprising nitrile in stream (A) or directly in the reactor wherein the component comprising nitrile is in the amount ranging from 0.01 wppm to 10 wppm relative to the ethanol and is capable to neutralize a part of the catalyst active site; and
g) optionally the temperature of the reactor is adjusted to increase the alcohol conversion, the olefin yield, or both.
3. The process according to claim 1 or 2 wherein the catalyst is selected among:
a crystalline silicate zeolite having a ratio SiA1 higher than 10,
a dealuminated crystalline silicate zeolite,
a phosphorous modified zeolite,
silica-alumina,
alumina,
silicated, titanated, zirconated or fluorinated alumina
or silico-aluminophosphates.
4. The process according to claim 1 or 2 wherein a part of the component introduced at step f) is already contained in the stream (A).
5. The process according to claim 1 or 2 wherein all the component introduced at step f) is already contained in the stream (A).
6. The process according to claim 1 or 2 wherein the component injected at step f) additionally comprises at least one from the group consisting of ammonia, organic ammonium salts, hydrazine, amines, amides, imines, di-imines, imides, cyanates, isocyanates, nitrites and nitroso compounds.
7. The process according to claim 1 or 2 wherein the component injected at step f) additionally comprises at least one from the group consisting of aldehydes, ketones and carboxylic esters.
8. The process according to claim 1 or 2 wherein the component injected at step f) additionally comprises at least one from the group consisting of thiols, sulphides and disulfides.
9. The process according to claim 1, wherein the component injected at step f) additionally comprises at least one from the group consisting of pyridines, pyrrols, pyrrolydones and pyrrolidines.
10. The process of claim 1, wherein the component injected at step f) additionally comprises at least one from the group consisting ammonia, organic ammonium salts, hydrazine, amides, imines, di-imines, imides, cyanates, isocyanates, nitrites, nitroso compounds, carboxylic esters, and thiols, disulfides.
11. The process of claim 1, wherein the component injected at step f) additionally comprises at least one from the group consisting ammonia, organic ammonium salts, hydrazine, amides, imines, di-imines, imides, cyanates, isocyanates, nitrites, and nitroso compounds.
12. The process of claim 1, wherein the stream (B) is fractionated to recover the unconverted alcohol, and the unconverted alcohol is recycled to the reactor of step a).
13. The process of claim 1, wherein the stream (B) is fractionated to recover the water and the olefin, and wherein a part of the water is recycled to the reactor of step a).
14. The process of claim 1, wherein the ethanol is a single alcohol introduced to the reactor.
15. The process of claim 1, wherein the temperature of the reactor is adjusted to increase the alcohol conversion, the olefin yield, or both.
16. The process of claim 15, wherein the temperature of the reactor is adjusted by increasing the temperature by an amount ranging from 5 to 50\xb0 C.
17. The process according to claim 1, wherein the catalyst is a dealuminated crystalline silicate zeolite.
18. The process according to claim 1, wherein the catalyst is a phosphorous modified zeolite made by a process comprising:
selecting a zeolite among the H+ and NH4+ form of MFI, MEL, FER, MOR, clinoptilolite, MWW, TON, EUO, MFS and ZSM-48, wherein the selected zeolite has a SiA1 ratio of 100 or lower;
steaming the selected zeolite at a temperature ranging from 400 to 870\xb0 C. for from 0.01-200 h;
leaching the steamed zeolite with an aqueous acid solution at conditions effective to remove a substantial part of Al from the steamed zeolite;
introducing phosphorous with an aqueous solution containing the source of phosphorous at conditions effective to introduce advantageously at least 0.05 wt % of the phosphorous;
separation of solid from liquid;
an optional washing step, an optional drying step, or an optional drying step followed by a washing step; and
a calcination step.
19. A process comprising:
a) introducing in a reactor a stream (A) comprising ethanol, optionally water, optionally an inert component,
b) contacting said stream (A) with an acidic catalyst in said reactor at conditions effective to dehydrate at least a portion of the alcohol to make a corresponding olefin having the same number of carbon atoms as the alcohol,
c) recovering from said reactor a stream (B) comprising the olefin, water and optionally the inert component and unconverted alcohol,
d) optionally fractionating the stream (B) to recover the optional unconverted alcohol and recycling said optional unconverted alcohol to the reactor of step a),
e) optionally fractionating the stream (B) to recover the optional inert component, the water and the olefin, and optionally recycling said optional inert component and optionally a part of the water to the reactor of step a),
wherein:
f) introducing a component comprising nitrile in stream (A) or directly in the reactor wherein the component comprising nitrile is in the amount ranging from 0.01 wppm to 10 wppm relative to the ethanol and is capable to neutralize a part of the catalyst active site; and
g) optionally the temperature of the reactor is adjusted to increase the alcohol conversion, the olefin yield, or both;
and wherein the component introduced at step f) further comprises at least one from the group consisting of hydrazine, amines, amides, imines, di-imines, imides, cyanates, isocyanates, nitrites and nitroso compounds;
or selected from the group consisting of aldehydes, ketones and carboxylic esters;
or selected from the group consisting of thiols, sulphides and disulfides.
20. The process according to claim 19, wherein the component introduced at step f) is introduced by
blending the component with the stream (A).
21. The process according to claim 19, wherein the component introduced at step f) is introduced by blending the component with a part of the stream (A) which is subsequently introduced in the reactor with a remaining part of the stream (A).
22. The process according to claim 19, wherein the component introduced at step f) is introduced by blending the component with the inert component which is subsequently introduced in the reactor with the stream (A).
23. The process according to claim 19, wherein the component introduced at step f) is introduced by blending the component with the water which is subsequently introduced in the reactor with the stream (A).
24. The process according to claim 19, wherein the component introduced at step f) is introduced by blending the component with a stream that is recycled back to the reactor comprising the unconverted alcohol, the water or the inert component.
25. The process according to claim 19, wherein the component introduced at step f) is introduced by blending an alcohol feedstock that is substantially free of the component with an alcohol feedstock containing the component.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
1. A method for purifying a contaminated solution, the method comprising:
receiving, via a contaminated solution feed, a contaminated solution, the contaminated solution including a greater concentration of undesired ions than desired ions and an untreated ratio of undesired ions to desired ions;
mixing the contaminated solution with an ion exchange purifying material having a higher affinity for the desired ions than the undesired ions;
removing the undesired ions from the contaminated solution by co-currently transporting the ion exchange purifying material with the contaminated solution so as to produce partially loaded ion exchange purifying material and a product solution that includes a treated ratio of undesired ions to desired ions, wherein the treated ratio is less than the untreated ratio, and wherein the co-currently transporting is limited to a transit time controlled so as to achieve only partial loading of the ion exchange purifying material, whereby loading of the undesired ions onto the ion exchange purifying material is greater than loading of desired ions onto the ion exchange purifying material;
separating the partially loaded ion exchange purifying material from the product solution;
discharging the product solution;
counter-currently mixing the partially loaded ion exchange purifying material with fresh regenerant so as to produce spent regenerant and ion exchange purifying material that is regenerated; and
transporting the ion exchange purifying material that has been regenerated in the direction of the contaminated solution feed to enable the receiving, the mixing, the removing, the separating, the discharging, and the counter-currently mixing to be continuously repeated.
2. The method of claim 1, including:
introducing rinse solution with the fresh regenerant and the ion exchange purifying material that is regenerated, wherein the rinse solution that is introduced is split into a rinse solution stream and a transport rinse solution, the rinse solution stream flows in the direction of the fresh regenerant and the transport rinse solution flows in the direction of the purifying material that is regenerated.
3. The method of claim 2, including:
discharging the spent regenerant at a rate that is the same as a flow rate of the fresh regenerant plus the fraction of the rinse solution that flows in the direction of the fresh regenerant.
4. The method of claim 3, including:
controlling a fraction of the rinse solution that reports to the transport rinse solution by controlling a resistance to the transporting of the purifying material.
5. A method for selectively removing contaminants from liquid using a continuously circulating stream of purifying media, the method including:
mixing a regenerated ion exchange purifying media, in a predetermined stoichiometric ratio, with a contaminated liquid containing at least desired contaminants and undesired contaminants, a concentration of the undesired contaminants being greater than a concentration of the desired contaminants, the ion exchange purifying media having a higher affinity for the desired contaminants than the undesired contaminants, the contaminated liquid having an untreated ratio of undesired ions to desired ions;
a. co-currently transporting the ion exchange purifying media and the contaminated liquid in a mixed state for a predetermined time;
b. removing, using the ion exchange purifying media, while co-currently transporting the ion exchange purifying media and the contaminated liquid, contaminants from the contaminated liquid so as to produce a mixture of a decontaminated liquid and a partially contaminated ion exchange purifying media, wherein the decontaminated liquid has a treated ratio of undesired contaminants to desired contaminants that is less than the untreated ratio, and wherein the co-currently transporting is limited to a transit time controlled so as to achieve only partial loading of the ion exchange purifying material, whereby loading of the undesired contaminants onto the ion exchange purifying material is greater than loading of desired contaminants onto the ion exchange purifying media;
c. separating the partially contaminated ion exchange purifying media from the decontaminated liquid;
d. contacting the partially contaminated ion exchange purifying media in counter current fashion with a regenerant solution so as to produce a regenerated ion exchange purifying media; and
e. returning the regenerated ion exchange purifying media to the mixing step, whereby the continuously circulating ion exchange purifying media selectively removes contaminants from the liquid.
6. The method of claim 5, wherein the predetermined stoichiometric ratio and the predetermined time are selected so as to achieve a desired degree of removal of one or more of the undesired contaminants.
7. The method of claim 5, where the predetermined stoichiometric ratio is achieved by controlling a circulation rate of the ion exchange purifying media.
8. The method of claim 7, wherein the circulation rate of the ion exchange purifying media is controlled by a hydrodynamic means and where the mixing, transport, separation and regeneration steps occur in a mixing process volume, a transport process volume, a separation process volume, and a regeneration process volume that are continuously open to each other.
9. The method of claim 8, wherein the hydrodynamic means of controlling the circulation rate of ion exchange purifying media is measurement and control of a hydrodynamic pressure difference across the transport process volume and the regeneration process volume.
10. The method of claim 9, wherein measurement of the hydrodynamic pressure difference across the transport process volume and regeneration process volume is accomplished by a means for measuring the pressure differential across an interval of the regeneration process volume, and near an exit point of the regenerated ion exchange purifying media from the regeneration process volume.
11. The method of claim 9, where the hydrodynamic pressure difference across the transport process volume and the regenerator process volume is controlled by a means for adjusting the hydrodynamic resistance of the transport process volume to a flow of the liquid and the ion exchange purifying media.
12. The method of claim 1, wherein the contaminated solution and the ion exchange purifying material are mixed in a predetermined stoichiometric ratio achieved by controlling a circulation rate of the ion exchange purifying media.
13. The method of claim 1, wherein the counter-currently mixing involves gravity moving the partially loaded ion exchange purifying material down while the fresh regenerant is moved against the force of gravity.
14. The method of claim 13, wherein both the contaminated solution and the ion exchange purifying material are transported co-currently against the force of gravity.
15. The method of claim 1, wherein the untreated ratio of undesirable ions to desirable ions is greater than one.
16. A method comprising the steps of:
co-currently mixing a contaminated solution with an ion exchange purifying material to produce a partially treated solution and partially loaded ion exchange purifying material, the ion exchange purifying material having a higher affinity for the desired ions than for the undesired ions, the partially treated solution having a treated ratio of undesired ions to desired ions, wherein the treated ratio is less than an untreated ratio of undesired ions to desired ions, the co-currently mixing limited to a transit time that prevents full loading of the ion exchange purifying material and enables greater loading of undesired ions onto the ion exchange purifying material than loading of desired ions onto the ion exchange purifying material; and
counter-currently mixing the partially loaded ion exchange purifying material with a regenerant solution thereby regenerating the ion exchange purifying material.
17. The method of claim 16, the step of co-currently mixing is carried out in a reactor, and wherein the transit time is controlled by a volume of the purifying material within the reactor at any given time.
18. The method of claim 16, wherein a loading of the ion exchange purifying material during the co-currently mixing is controlled by a flow rate of the ion exchange purifying material.