METHODS FOR MONITORING AND CONTROLLING CONTAMINANTS IN FOOD PROCESSING SYSTEMS
20200172988 ยท 2020-06-04
Inventors
- John K Burchtorf (Glen Allen, VA, US)
- Megan PETTYGROVE (Glen Allen, VA, US)
- William H Henderson (Glen Allen, VA, US)
Cpc classification
C13B20/005
CHEMISTRY; METALLURGY
International classification
Abstract
A method for determining the lignin or lignin by-product content of a process stream includes measuring the fluorescence parameter of a fluorescence spectra of the process stream, comparing the measured fluorescence parameter with predetermined a fluorescence parameter of lignin or lignin by-product reference samples, determining the amount of lignin or lignin by-product based on the comparison with the reference samples. Lignin or lignin by-products can then be removed from a process stream by adding a sufficient amount of a compound suitable for precipitating the lignin or lignin by-product to the process stream, and removing the precipitated lignin or lignin by-product from the process stream.
Claims
1. A method for controlling an amount of an anionic contaminant in a stream of a sugar processing system, the method comprising: determining an amount of the anionic contaminant in the stream using a fluorescence parameter or cationic demand parameter of the anionic contaminant, the anionic contaminant selected from at least one of the group consisting of lignin, a lignin by-product, tannin, and a tannin by-product; and controlling an amount of the anionic contaminant in the stream based on the determined amount of the anionic contaminant in the stream.
2. The method for controlling the amount of anionic contaminant according to claim 1, wherein the amount of the anionic contaminant is determined in a thin juice stage of the sugar beet processing system.
3. The method for controlling the amount of anionic contaminant according to claim 1, wherein the anionic contaminant is the lignin by-product or the tannin by-product, and the amount is determined downstream of a thin juice stage of the sugar beet processing system.
4. The method for controlling the amount of anionic contaminant according to claim 1, wherein the anionic contaminant is undetectable using the fluorescence parameter or the cationic demand parameter before a thin juice stage of the sugar beet processing system.
5. The method for controlling the amount of anionic contaminant according to claim 1, wherein controlling the amount of the anionic contaminant in the stream includes removing at least some of the anionic contaminant from the stream.
6. The method for controlling the amount of anionic contaminant according to claim 5, wherein removing the at least some of the anionic contaminant from the stream includes destroying, neutralizing or precipitating the anionic contaminant.
7. The method for controlling the amount of anionic contaminant according to claim 6, wherein removing the at least some of the anionic contaminant from the stream includes precipitating the anionic contaminant by adding a sufficient amount of a precipitator compound configured to precipitate the anionic contaminant from the stream.
8. The method for controlling the amount of anionic contaminant according to claim 5, wherein the removing step occurs upstream of a boiler stage in the sugar processing system.
9. A method for determining a content of an anionic contaminant in a stream of an industrial processing system, the method comprising: measuring a fluorescence parameter or cationic demand parameter of an anionic contaminant in the stream, the anionic contaminant selected from at least one of the group consisting of lignin, a lignin by-product, tannin, and a tannin by-product; comparing the measured parameter with that of a premeasured parameter ofanionic contaminant reference samples; and determining the amount of the anionic contaminant based on the comparison with the reference samples.
10. The method for determining the content of anionic contaminant according to claim 9, wherein the anionic contaminant is at least one of the lignin or the lignin by-product.
11. The method for determining the content of anionic contaminant according to claim 9, wherein the anionic contaminant is at least one of the tannin and the tannin by-product.
12. The method for determining the content of anionic contaminant according to claim 9, wherein the amount of the anionic contaminant in the stream is controlled to a predetermined threshold, and the predetermined threshold corresponds to an acceptable amount of surface fouling in the processing system.
13. The method for determining the content of anionic contaminant according to claim 9, wherein the anionic contaminant is selected from at least one of lignin by-product and tannin by-product.
14. The method for determining the content of anionic contaminant according to claim 13, wherein the fluorescence parameter or the cationic demand parameter is measured in the processing system downstream of a stage that adds heat to the stream.
15. The method for determining the content of anionic contaminant according to claim 9, further comprising measuring the fluorescence parameter or the cationic demand parameter of at least two anionic contaminants in the stream.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF EMBODIMENTS
[0037] Disclosed embodiments include methods for controlling an amount of an anionic compound in water of an industrial processing system, as shown in
[0038] Disclosed methods are applicable to any industrial processing system and include food or vegetable processing or pulp processing systems that contains fluorescent signatures or anionic compounds with cationic demand. Examples include, but are not limited to, sugar beet, sugar cane, carrot and potato processing systems that process the foods or vegetables.
[0039] By using fluorescence to track naturally occurring contaminants such as lignin or lignin by-products that result from the breakdown of lignin, the quality of the liquid stream can be evaluated and adjustments to various chemical additives to the liquid stream made to compensate for deteriorating or improving quality of the process or waste stream that is being monitored.
[0040] In the case of sugar (sucrose) processing facilities, lignins are released into the process streams from the sugar beet or cane. As quality of the supply of sugar beet or cane degrades (due to infections, storage conditions, age of beets), higher levels of lignins are realized in the process streams. Because the lignins are anionic in charge due to the presence of phenolic hydroxyl groups, they impose a cationic demand to neutralize in order to provide the best possible purification of the liquor or juice of mineral salts, color bodies and non-sugars.
[0041] Waste streams can also contain lignins that impart an anionic charge to the waste stream which can interfere with clarification of the waste stream. The fluorometer can be utilized to identify and quantify the amount of lignin in the stream and programmed to control additions of chemicals and reagents to eliminate the impact of the lignin from impairment of processing the process or waste stream.
[0042] Cation demand tests conducted during fair and poor quality of sugar beet processing show an increased level of cation demand during test periods for poor quality beets as opposed to that of fair quality beets. In the purification of the juice stream, cation demand during poor beets exhibited a reduction of demand from a peak of 26 ppm in raw juice to 1.5 ppm exiting the purification process (2nd carb filters).
[0043] Disclosed embodiments include methods for determining contamination of boiler supply water from evaporator condensate. Beet quality with regard to the amount of contaminants present in the beet may vary according to the time of the season when the beets are harvested, and generally, beet quality decreases later in the season. During processing, these contaminants carry through the thin juice.
[0044] Thin juice is the fluid containing dissolved raw sugar. In some processes, the thin juice may have between 12.5-13.5% solids. In other processes, thin juice has from 13 to 16%, Usually, the solids comprise about 90% sugar. However, these parameters can vary depending on the process and facility, condition of the beets, climate, water levels, draft for diffusion and brix adjustments due to processing dynamics at the time. The quality of the beets can vary hour to hour and day to day depending on the storage conditions of the beets. The condition of the beets is critical because as the beet quality degrades, the cellulose structure/integrity allows for increased lignin to be released in the diffusion process.
[0045] In some processes, the thick juice has around 50-60% solids, with 90% being sugar. In other processes, the thick juice may have from 58-62% solids. As with thin juice, these parameters can vary.
[0046] As the thin juice goes through the evaporator stages, more contaminant will foul evaporators. The lignins or contaminants at least partially are modified to allow volatilization in the evaporators and are carried in the vapor from one body of the stream and supplied to the next body as the heat (or steam) source to continue evaporation of the next evaporator body. This vapor is condensed, carrying the lignins or contaminants to the boilers in the boiler feedwater. The lignins or contaminants then can be volatilized and carried out in the boiler steam.
[0047] In one embodiment, the method utilizes fluorescenc spectroscopy to quantify process contamination of a condensate so that operators may be alerted and act accordingly. Baseline levels for the alarm set point increase rather dramatically with poor beet quality. If the alarm is set at a certain threshold, the poor beet quality will cause contaminants to breach that threshold if nothing is done, but this process will allow you to react and prevent fouling of the evaporators.
[0048] Analysis of juice streams has shown various levels of lignin in process streams and condensate streams.
[0049] Four samples of various sugar beet processing liquids from Amalgamated Sugar (Boise, Id.) were analyzed. The first carb sample occurs right after the hot limer and is maintained ata pH from 10.9 to 11.1. After clarification, second carb, and filtration, thin juice is obtained.
[0050] In other embodiments, a cossette mixer is arranged between the slicer and the diffuser. The diffusers (2) are tower diffusers. After 1st carb (carbonation) there is a clarifier to settle the suspended solids with the overflow feeding 2nd carb. The outflow from 2nd carb goes to filters (normally industrial leaf filters), then softening. After softening, the juice becomes evaporator supply or thin juice. The thin juice goes through a 7 effect evaporator train where in general terms the sugar content goes from 14% (brix) to 60% (brix) to become thick juice. During poor beet quality conditions, there was 3-3.5% lime on beets and 1-3 ppm of coagulant (P823L) to improve purification and settling performance.
[0051] The process from the start (slicing) to thick juice is referred to as the beet end. The rest of the process (pans, standard liquor filters, high green, low raw, white pans, crystallizer, spinners, granulators, etc, is termed the sugar end of the factories. Any lignins and tannins or other contaminants that make it through to thick juice will end up in the molasses stream of the sugar end.
[0052] The sample of thin juice had a pH of 6.7.
[0053] The thin juice is sent to multiple evaporators to remove liquid of the juice to form a sugar-containing concentrate. The condensate from the first evaporation was labeled first drip and the condensate from the second evaporation, labeled second drip.
[0054] 3D fluorescence scans taken from each sample show how fluorescence changes throughout the system. The initial fluorescence scans show the impurity present in the 1st carb and thin juice (lignins, tannins, etc.). The 3D fluorescent graphs show the excitation and emission of the initial contaminant. This is also demonstrates how pH change alone is not sufficient to cause breakdown of the contaminant. As we have shown, under the evaporator conditions, the contaminant breaks down into a different species (1st drips, 2nd drips), noted by the change in fluorescence. These breakdown products have a lower excitation and emission. That breakdown product either has a low enough boiling point or can sublime, and is carried through the evaporator into the condensate.
[0055] The excitation and emission maxima showed similar results for the first carb and thin juice, but changed dramatically in the 1st drips and again in the 2nd drips. Fluorescent intensity can be related to concentration.
TABLE-US-00001 TABLE 1 Fluorescence excitation and emission maxima for samples. Excitation Emission Sample (nm) (nm) Carb Juice 404 482 Thin Juice 388 474 1st Drips 274 334 2nd Drips 266, 302 332, 336
[0056] Lignins and tannins are responsible for the fluorescence in the 1st carb and thin juice. The fluorescent compounds in the 1st drips and 2nd drips must be of significantly lower Mw as compared to the initial contaminant and nonpolar or have the ability to sublime in order to make it to the evaporate condensate. Lignins and tannins can have varying Mw and be made of a lot of different components.
[0057] The evaporation conditions were substantially reproduced in this test by distilling the thin juice in a rotary evaporator at 80 C. under reduced pressure. After thin juice had been distilled to approximately 50% of its starting volume, fluorescence of the distillate and the pot were measured again.
[0058] After replicating the evaporator conditions, the excitation and emission maxima of the fluorescence of the condensate Obtained by rotary evaporation (304 ex, 340 em) was similar to the 1st drips obtained above in the process of the four samples, and similar to one of the fluorescence maxima from the 2nd drips. The fluorescence spectra obtained from evaluating the pot resembled the fluorescence spectra of the initial thin juice. Thus, the evaporator conditions in the lab may be replicated to show that the contaminant breaks down and can be carried to the condensate under evaporator conditions.
[0059] These results show that contaminants are carried through the first carp process and that these contaminants or breakdown products can result in contamination of evaporators and boilers further down in the process.
[0060] By monitoring for these compounds (through fluorescence and/or cation demand) chemical treatment feeds can be adjusted or mechanical removal methods used to adequately remove contaminants as quality of the organic matter increases or decreases in quality. Additional coagulants, flocculants or other or water treatment chemicals can be used to remove excess contaminant.
[0061] Beet sugar processing utilizes copious amounts of CaO or lime for purification of the raw juice (stream off the diffuser) stream. In one cation demand test, there was a demand of 26 ppm (poor quality beets) in the raw juice off the diffuser and dropped to 7-9 ppm through the liming stages and further to 2-4 ppm through 1st carbonation. Samples taken after 2nd carbonation filtering were still at 2 ppm.
[0062] Lime reduces the demand either by destruction, charge neutralization or precipitation. The ability to determine this demand in real time may allow the factories to vary lime addition by the proper amount needed to achieve optimal purification. Any remaining demand can be neutralized with the addition of an approved coagulant (P823L) automatically from determination of demand from the subject patent process.
[0063] Approved flocculation polymers are anionic in nature. The presence of an anionically charged compound such as lignin can prevent proper settling and clarification of the juice stream. Other issues include turbidity of overflow, high color imparted by lignin, tannin and other color bodies, and poor filtration performance.
[0064] The values and ranges of fluorescence in the graphs can be used to monitor contaminants and breakdown products. The concentrations can be quantified based on relative excitation and emission intensities, but not absolute values at this time.
[0065] This above monitoring process may also be used in the pulp or paper industry in wood products wastewater stream such as paper and pulp streams. In paper processing, calcium and aluminum compounds are used to neutralize and precipitate lignin in the bleaching water of chemical pulp (CA2573035C). Calcium is known to precipitate lignin.
[0066] This same process can help determine demand from the lignin for coagulants and other reagents to improve performance of beet and potato flume clarifiers, and vegetable waste water streams.
[0067] The advantages of disclosed embodiments include, but are not limited to: consistency of purification of the subject stream under a wide range of operating conditions, enhanced settling and removal of suspended solids. (reduced turbidity of overflow), improved elimination of non-sugars and color bodies imparted by the lignins and tannins, improved filtration performance and dewatering, higher process throughput from 1-4 above, improved quality and purity of the process stream from improved contaminant elimination, improved final product production rates during poor quality stream conditions, cleaner boiler and steam system through reduction in fouling contaminants (if applicable), improved conformance to discharge requirements (if applicable), and automation of the evaluation process.
EXAMPLES
[0068] Prototype fluorescent probes were built to measure the fluorescent breakdown products at beet sugar factories. The prototypes were installed on 2.sup.nd evaporator drips (1.sup.st vapor). The units were equipped with a sample cooler, high sample temperature shutoff, wireless wifi modem for remote access an alarm and a CIP system if needed.
[0069] The factories had undergone a significant upsizing immediately before the campaigns. Beet quality was very poor, in the range of 82-83% purity. Background fluorescence of condensate was identified and scaled with alarm points determined to alarm at 0.01% juice relative to contaminate level in the condensate. The PLC could be accessed remotely to fine tune the prototype. However, supervisors manned the units for over a week to gather data and make changes as necessary quickly.
[0070] Operating conditions and kinks due to factory modifications provided ample opportunity to verify alarm reality. Several alarms were recorded during the first few days with varying level of severity. Most were small, short lived and some were moderate, short lived. Verification tests were to be alpha napthal and refractometer if high enough. No events were of length to verify sugar levels, but the moderate event effect manifested verification in loss of boiler alkalinity and pH depression. The prototypes were allowed to run for almost 2 months to provide data and warnings to operation personnel. This also allowed tuning and adjustments to be made remotely while downloading of data points and trend information.
[0071] The outcome of the field tests were successful in the respect that the unit ran and provided reliable data and did not require cleaning or calibration for that test period. Previous experience with similar monitors require regular cleaning and calibration as well as frequent false alarms.
Example 1
[0072] This example is from a facility that processes sugar beets. Because non-sugars are decreased through the 1.sup.st and 2.sup.nd carb purification process, which uses lime and flocculant, studies were initiated by using a testing protocol to model canon demand. Samples were tested from several locations such as raw juice, liming, carbonation, 1.sup.st carb clarifier overflow, and 2.sup.nd carb filtrate. There was a significant cation demand in the raw juice (26 ppm) followed by a drop in demand through purification, giving evidence that the non-sugar impurities are likely anionic. The final sample of 2.sup.nd carb filtrate still indicated a 2 ppm cation demand. The presence of the cation demand accompanied by persistence through the purification process helped inventors to focus in on potential species that have an anionic charge. Using 3D fluorescence, inventors identified the fluorescent non-sugar species as lignins and tannins, which are not typical compounds tested for in most industry methodology. A 3D fluorescence spectrum for 1.sup.st carb (
[0073] The fluorescence spectrum for both first carb and thin juice shows a broad excitation from 380-470 and emission from 440-540 with an excitation/emission maxima at 395/480. The diagonal line running across the spectra is an artifact from excitation wavelengths that are not fully absorbed and therefore measured on the emission spectrum. It is apparent, that the fluorescence intensity decreases after the carbonation stage, further indicating that dissolved non-sugars are removed during the carbonation process. A similar spectrum is shown for cane sugar production in
[0074] From this data, inventors were able to pinpoint an excitation and emission wavelength to track pH, lignins and tannins, nitrates, nitrites, P alkalinity and M alkalinity throughout the purification process. The profiles of two seperate tests are illustrated in Tables 2 and 3, respectively, below.
TABLE-US-00002 Tannin Lignin Nitrate Nitrite P M Sample # Sample Name pH (mg/L) (mg/L) (mg/L) Alkalinity Alkalinity 1 Rotary Screen Influent 4.44 280 0.53 9.1 2 Pre-limer Cell 1 5.43 350 1 5 1094 3 Pre-limer Cell 4 10.32 300 130 2.5 822 1783 4 Pre-limer Cell 5 11.31 250 116 11 1906 3834 5 Pre-limer Cell 6 11.74 250 124 13 4402 6848 6 Pre-limer Outlet 11.76 260 143 5 4656 6956 7 Cold Limer Effluent/Outlet 11.89 270 110 9.9 6530 8996 8 Hot Limer Effluent/Overflow 12.07 260 116 16 11472 13330 9 1st Carb Effluent/Overflow 11.17 190 110 29 1344 2516 10 Pultsch Mud Supply 11.23 180 108 12 1536 2950 11 Pre-limer Sludge Recycle 4.30 370 0.63 2.5 12 DORR Clarifier Effluent Clear 11.04 160 103 12 1188 2228 Overflow 13 Pre-limer Recirculation Sludge 11.20 160 100 12 1452 2574 14 2nd Carb, 1st Body 8.94 160 80 19 139 889 Effluent/Overflow 15 2nd Carb Retention Supply 8.61 215 107 13 55 852 16 2nd Carb Retention Overflow 9.22 215 0.82 2.5 261 1191 17 2nd Pass Filter Effluent 9.10 205 50 5 214 1239 18 Softener Supply Tank 9.17 215 3.7 80 251 1252 19 Softened Juice 9.11 215 110 12 217 1203 20 Sulfur Tower Effluent 8.91 220 103 5 178 1137 21 Sulfured Juice Tank 8.93 326 100 5 175 1130 22 Flume Water 11.58 220 47 39 1563 1644 23 1A Evaporator Drips 10.14 1.3 0.1 0.5 235 280 24 1B Evaporator Drips 10.10 1.1 0.1 0.5 179 213 25 2B Evaporator Drips 9.92 3.2 0.1 0.5 563 735
TABLE-US-00003 Tannin Lignin Nitrate Nitrite P M Sample # Sample Name pH (mg/L) (mg/L) (mg/L) Alkalinity Alkalinity 1 Raw Juice 4.36 330 1.1 2.5 0 0 2 DORR Clarifier Influent 11.14 250 214 9 806 2454 3 DORR Overflow 11.22 200 186 5 1094 2305 4 DORR Mud Pump underflow to 11.43 250 200 7.3 1946 4030 Putsch 5 Thin Juice 8.87 190 211 18 181 1380 6 Thick Juice 8.19 480 975 10 0 3951 7 Clarifier Influent 4.88 160 6.8 5 0 1385 8 Clarifier Over flow 4.99 140 22 5 0 1320 Clarifier Underflow 6.11
[0075] As seen in FIGS, 5A and 5B, in order to remove the non-sugars, lime is added to raw juice to raise the pH to around 11-12 which helps facilitate coagulation of particulates and non-sugars. At the carbonation stages, the pH is dropped by adding CO.sub.2 to help solids precipitate. From the Don or clarifier overflow after 1.sup.st carbonation, the juice is sent to another carbonation step or 2.sup.nd carb. After filtration, the juice is referred to as thin juice. The thin juice goes through five to seven evaporator stages, which concentrate the juice into thick juice.
[0076] Initial testing after the diffuser gives the highest amount of lignin and tannin. The tannins and lignins steadily decrease throughout the purification process until the evaporator drips when most of the lignins and tannins are removed, as seen in
[0077] Despite the condensate, which is used as boiler feedwater, having no sugar as verified by refractometry and field Alpha Napthal testing, or tannins and lignins, it continued to foul standard liquor (3.sup.rd) filters downstream indicating that additional undetected contaminants were present. In order to verify field results, the 1.sup.st (
[0078] The fluorescence spectra shown in
[0079] These results clearly indicate a previously undetected contaminant that is not present in the thin juice. Inventors theorized that this contaminant could be a breakdown product from the tannins and lignins found throughout the rest of the process. In order to test this theory, the thin juice, containing tannins and lignins, was submitted to a simulated evaporator process under reduced pressure at 80 C. During the lab experiment we were able to see 2.5 similar results seen in the field, with the simulated 1.sup.st evaporator drips (distillate) having an intense fluorescence spectrum with a maximum excitation/emission at around 300/335, as shown in
[0080] These results verify that the fluorescent species remaining in the thin juice after purification are thermally unstable, giving breakdown products which also fluoresce, albeit at a different wavelength. Due to the change in excitation/emission properties, these breakdown products would remain undetectable using a fluorometer that measured tannins and lignins found throughout the rest of the process. Additionally, these breakdown products are volatile enough to contaminate evaporator condensate and may be contributing to fouling in evaporator demisters and damage to boilers from pH excursions.
[0081]
Example 2
[0082]
Example 3
[0083]
[0084] These results verify the presence of non-sugar contaminants in beet and cane sugar purification processes which contribute to boiler feedwater contamination and boiler upsets through an unexpected breakdown mechanism. These contaminants can be measured using fluorescence and cationic demand. Disclosed embodiments provide surprisingly beneficial methods for utilizing fluorescent and cationic demand probes for controlling contamination.
[0085] It will be appreciated that the above-disclosed features and functions, or alternatives thereof, may be desirably combined into different systems or methods. Also, various alternatives, modifications, variations or improvements may be subsequently made by those skilled in the art, and are also intended to be encompassed by the disclosed embodiments. As such, various changes may be made without departing from the spirit and scope of this disclosure.