EP0040473A1 - Reinigung hydrolysierter Stärke - Google Patents

Reinigung hydrolysierter Stärke Download PDF

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Publication number
EP0040473A1
EP0040473A1 EP81301807A EP81301807A EP0040473A1 EP 0040473 A1 EP0040473 A1 EP 0040473A1 EP 81301807 A EP81301807 A EP 81301807A EP 81301807 A EP81301807 A EP 81301807A EP 0040473 A1 EP0040473 A1 EP 0040473A1
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EP
European Patent Office
Prior art keywords
syrup
floc
process according
ppm
aluminium
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Granted
Application number
EP81301807A
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English (en)
French (fr)
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EP0040473B1 (de
Inventor
John Trethowan Rundell
Paul Richmond Pottage
Ronald James Harradine
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Tate and Lyle PLC
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Tate and Lyle PLC
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    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K1/00—Glucose; Glucose-containing syrups
    • C13K1/06—Glucose; Glucose-containing syrups obtained by saccharification of starch or raw materials containing starch
    • C13K1/08—Purifying

Definitions

  • the present invention relates to the clarification of hydrolysed starch syrups.
  • Hydrolysis of starch gives a syrup containing a variety of saccharides, including glucose.
  • the hydrolysis is effected using acid and/or enzyme procedures. These procedures are well documented in the patent and other literature, and are practised on an industrial scale. It is thus unnecessary to describe them now in detail.
  • starch from a natural source such as maize (i.e. the cereal known in the USA and elsewhere as 'corn'), is usually liquefied and thinned using hydrochloric or other acid, or using an enzyme preparation containing an ⁇ -amylase.
  • the thinning can give a syrup of up to 50CE or sometimes higher ("fE” or "Dextrose Equivalent” being the percentage of solids present as reducing sugars and determined as equivalents of dextrose), but, in order to obtain DEs above about 45DE, it is customary to effect a saccharification using an enzyme preparation typically containing an amylo-glucosidase.
  • fE or "Dextrose Equivalent” being the percentage of solids present as reducing sugars and determined as equivalents of dextrose
  • it is customary to effect a saccharification using an enzyme preparation typically containing an amylo-glucosidase it will be appreciated that for syrups of high DE, say 60 DE or above, it is essential to employ an
  • the crude syrup obtained as product will contain impurities derived from the original starch source.
  • a crude syrup from maize i.e. a crude corn syrup
  • Similar impurities are encountered in hydrolysed starch syrups derived from other starch sources, such as wheat or potatoes.
  • This earlier invention is applicable to a wide range of processes requiring the separation of suspended solids from an aqueous liquid, for example in brewing, water purification treatments, the treatment of sewage and industrial effluents, and mineral ore separation processes.
  • the invention is particularly useful for separating suspended solids from sugar liquors, syrups or juices, during the various stages of sugar manufacture.
  • the retention-flocculation process can be used, for example, in the manufacture of sucrose, but this is not the only sugar to whose manufacture it can be applied. More specifically, the retention-flocculation process can be useful for separating suspended solids from hydrolysed starch syrups.
  • the present inventors have been investigating this application of the retention-flocculation process to the clarification of hydrolysed starch syrups, and in so doing have developed an improved process which offers specific advantages over the process known from UK Patent Specification No. 1,397,927.
  • the new processes can be generally applied to the clarification of hydrolysed starch syrups, and in particular to high DE glucose syrups prepared by the acid-enzyme or enzyme-enzyme procedures ("High DE Syrups”) and to low DE glucose syrups prepared by acid or enzyme liquefaction and thinning without the subsequent enzyme saccharification (“Low DE Syrups").
  • a novel process for the clarification of a hydrolysed starch syrup comprises forming in the syrup, at a pH cf 3.5 to 6.5, a primary floc formed between aluminium ions, hydroxide ions and phosphate ions; aerating the syrup containing the primary floc; distributing an anionic organic polymeric flocculant through the aerated syrup, to initiate thiformation of a secondary floc; allowing the secondary floc to grow, and to segregate by flotation; and separating flocculated solids from clarified syrup.
  • the present invention is founded upon the discovery that there is a particular reagent system - aluminium ions/hydroxide ions/phosphate ions/pH 3.5 to 6.5 - which gives a primary floc optionally capable of entraining unwanted material from hydrolysed starch syrups.
  • This reagent system is different from those in our UK Patent Specification No. 1,397,927 and gives rise to a basic aluminium phosphate floc. It is this floc which is especially suited for removing from crude hydrolysed starch syrups the proteinaceous and other matter which it is difficult to remove completely using the known retention-flocculation process.
  • the present process can offer the following advantages:
  • the aluminium ions are preferably added as aluminium sulphate, though this is not critical, and other aluminium compounds, for example potassium aluminium sulphate or aluminium chloride, can be used.
  • the ion ratio of aluminium ions to phosphate ions is typically more than 1:1, with a ratio of more than 3 aluminium ions to 1 phosphate ion being particularly common.
  • the amounts of added aluminium (calculated as aluminium and expressed as ppm on weight of syrup) will lie in the range 5 to 100 ppm, preferably 20 to 40 ppm.
  • Crude hydrolysed starch syrups often contain residual levels of free phosphate, and it is not always necessary to add all of the phosphate ion required for formation of the floc. Indeed, for some phosphate-containing syrups it may not be necessary to add any phosphate ions at all.
  • a simple quantitative analysis of the crude syrup before adding phosphate ions permits due allowance to be made for any phosphate ions already present. As a general rule it is unnecessary to make allowance for aluminium ions already present since the crude syrups usually contain less than 1 ppm of aluminium. Where insufficient phosphate ions are present for reaction with the aluminium, it is preferred to raise the level to up to 50 ppm, more preferably 25 ppm of phosphate ions (calculated as P 2 05 and expressed as ppm on weight of syrup) by adding phosphate.
  • Phosphate ions are preferably added as phosphoric acid, though again other phosphate compounds, for example sodium phosphate (Na 2 HP0 4 ) can be used.
  • Low CE Syrup produced from starch by the acid hydrolysis procedures typically has a pH around 1 to 3, and in accordance with the present process, it is essential to adjust the pH to lie within the range of 3.5 to 6.5 for formation of the primary floc.
  • the adjustment of pH is preferably effected in two stages with intervening addition of the aluminium ions and, if needed, phosphate ions. Firstly alkali is added to stop the hydrolysis reaction and to effect a crude adjustment of the pH to, say, pH 4.5; secondly the aluminium and phosphate ions are added; and, thirdly, further alkali is added to effect a fine adjustment to the desired pH of, say, 4.5.
  • the pH adjustment is most conveniently carried out by adding sodium carbonate solution. However, other reagents, e.g. sodium hydroxide, can be used.
  • Low DE Syrup produced from starch by enzyme hydrolysis procedures typically has a pH around 6 to 7.
  • it is preferred first to add the aluminium and phosphate ions, thereby giving a pH of about pH 5.
  • acid such as hydrochloric acid is added to gain the desired pH of s.ay pH 4.5.
  • High DE Syrup produced from starch by acid-enzyme dual procedures or by enzyme-enzyme procedures typically has a pH of around 4 to 5 and any pH adjustment is preferably best effected by addition of the intended amount of aluminium and phosphate ions, followed by alkali as required to gain the desired pH.
  • the pH should lie within the range of 3.5 to 6.5 during the formation of the primary floc. It is most noticeable that an effective clarification is not obtained if the pH lies outside this range during growth of the primary floc. For best results, a pH of 4 to 5 is appropriate, especially about pH 4.5 to 4.7.
  • the syrup is aerated. Aeration is preferably carried out using agitation as described in our U.K Patent Specification No. 1,397,927. Aeration can be carried out directly on the syrup containing the primary floc, or on another liquid which is then added to the floc-containing syrup. In a preferred process, part of the clarified syrup produced by the process is itself aerated and added back to the floc-containing syrup, thereby indirectly effecting the desired aeration. For example, from 10 to 50%, usually 15 to 30% of the clarified syrup can be diverted from the product stream, aerated, and added to the incoming stream of floc-containing syrup.
  • an anionic organic polymeric flocculant is distributed therethrough to initiate the formation of a secondary floc.
  • Suitable flocculants are widely available and include the anionic polyacrylamides, particularly those with a molecular weight above 1,000,000. Especially preferred are the anionic polyacrylamides with a molecular weight of 5,000,000 to 10,000,000 and having a charge density of 20 to 75% by weight acrylate units, such as the anionic polyacrylamides sold under the Registered Trade Marks "TALOFLOTE" and "TALODURA".
  • TALOFLOTE Registered Trade Marks
  • TALODURA Registered Trade Marks
  • the secondary floc is then allowed to grow, and to segregate by flotation.
  • the growth and segregation is achieved by retaining the mixture in a flocculator vessel with non-turbulent agitation preventing the segregation of the secondary floc and thereby allowing it to grow, transferring the syrup with minimal agitation from the flocculator vessel to a separator vessel, and then allowing the secondary floc to segregate by flotation from the syrup.
  • Suitable equipment comprises a "TALO" (Registered Trade Mark) clarifier available from Tate & Lyle Ltd; such clarifiers represent apparatus as described and claimed in the U.K Patent Specification No. 1,397,927. Suitable residence times and other operating conditions are also described in No. 1,397,925.
  • the flocculated solids are separated from clarified syrup.
  • the separation may be effected by employing different outlets in the separator or other vessel containing the syrup and solids (as in a TALO clarifier), or by withdrawing first the syrup and then the solids using a common outlet: the former is more appropriate for continuous operation whereas the latter is more appropriate for batch operation.
  • This Example is based on experimental work carried out at a factory in Germany which had previously used a conventional 2-stage filtration to clarify the corn syrup.
  • a vessel 10 for preparation of starch slurry was equipped with a stirrer 11 and inlets 12, 13 and 14 respectively for starch, water and hydrochloric acid.
  • a pipe 15 led to an acid converter 16 of conventional construction.
  • A-pipe 17 then led to a flash tank 19, with pipe 18 being provided for addition of sodium carbonate solution to liquid in pipe 17.
  • a pipe 20 led to a buffer tank 21 equipped with a stirrer 22 for uniform mixing of the neutralised syrup.
  • a pump 23 was provided to pump the syrup through pipe 24 to inlet 36 of a reaction tank 28.
  • Pipe 25 served for addition of premixed aluminium ion/phosphate ion reagent to the syrup in pipe 24.
  • the reaction tank 28 had a stirrer 35, an inlet 26 for feeding in of sodium carbonate, and an outlet for gravity feeding of the syrup through a pipe 27 to a TALO clarifier 29.
  • This clarifier 29 was of substantially the same construction as the apparatus shown in Figure 2 of UK Patent Specification No. 1,397, 9Z7 and further description is not needed in the present specification.
  • a feed 30 was provided for addition of polyacrylamide flocculant (TALOFLOTE A5 solution, molecular weight about 7,000,000 and charge density about 47% acrylate) to liquid flowing into the clarifier 29.
  • Liquid separated from the clarifier was mainly drawn off by pipe 34, though there was a recycle loop 31 with centrifugal pump 32 permitting part of the clarified syrup to be aerated and returned to the stream entering the clarifier.
  • the clarified syrup drawn off through pipe 34 passed to a clarified syrup tank 36.
  • starch from inlet 12 and water from inlet 13 was mixed in the stirred vessel 10 to produce a uniformly mixed slurry (about 35% w/v).
  • a small amount of sodium metabisulphite was added at this stage to improve the colour of the final syrup.
  • hydrochloric acid 11 N HC1
  • the acidified slurry pH about 1.5
  • the slurry was heated to 125°C and the starch converted to sugars in about 10-15 minutes, giving a syrup of 42DE.
  • a small amount of sodium carbonate was then added in known manner through pipe 18 to the syrup during passage of the syrup to the atmospheric flash tank 19 where it was flash-evaporated to 105°C. Carbon dioxide bubbled off from the syrup during the flash arising from the decomposition of the carbonate.
  • the acid conversion can be replaced by an enzyme conversion. Conversion then takes place in the presence of enzyme at 106°C and at pH 6.2, and may be followed by an additional enzyme conversion at 60°C (saccharification) to a higher DE syrup. Acid, enzyme, acid-enzyme and enzyme-enzyme conversions are all possible.
  • Clarification in accordance with the invention was initiated by the formation in the reaction vessel 28 of a primary aluminium hydroxy-phosphate floc. This floc was produced by the dosing of aluminium and phosphate ions through inlet 25. Aeration of the primary floc was achieved indirectly by aeration of recycled syrup in the loop 31 using aeration pump 32. Aeration was followed by addition through feed 30 of the anionic polyacrylamide flocculant forming a secondary floc which was retained within the liquor with non-turbulent agitation for sufficient time (about 2 minutes) to allow the floc to grow in the way described in UK Patent Specification No. 1,397,927.
  • the floc-containing liquor flowed into a separator chamber of the clarifier 29, and the secondary floc floated to the surface as a scum.
  • the floated floc containing proteins and fats was removed as a scum by a rotary scraper blade and drawn off through pipe 33.
  • the clarified syrup was fed to a tank where carbon and filter aid were added, and the syrup was then filtered using six plate-and-frame filters. The process was operated so as to give a 42CE syrup of essentially the same clarity as had previously been obtained by the conventional method, that is, a syrup of about 20 ppm turbidity.
  • This Example is based on experimental work carried out at a factory in the USA.
  • the equipment was substantially as shown in the accompanying drawing, except for two modifications. Firstly, the acid converter 16 and associated equipment was replaced with conventional equipment for carrying out a dual enzyme-enzyme hydrolysis to give a high DE syrup. Secondly, at the junction between the pipe 27 from the reaction tank 28 and the return loop from the centrifugal pump 32, a holding tank was installed to even out flow into the clarifier 29.
  • the enzyme-enzyme converter was operated in conventional manner to produce 97DE syrup containing about 35% by weight of dissolved solids.
  • the syrup contained 0.5% suspended solids and was thus very turbid.
  • the solids themselves comprised about 25% oil and fat, about 22% protein and about 3% fibre and other matter.
  • the syrup contained about 116 ppm of phosphate and about 0.2 ppm of aluminium.
  • the syrup then passed through the holding tank to the clarifier 29. 7 parts by volume per minute of a 0.1% solution of TALOFLOTE A5 was metered in through the line 30. Clarified syrup was continuously drawn off through the pipe 34 and through the recycle loop 31. 30% the syrup (by volume of syrup passing through the clarifier) was drawn off through the loop 31, aerated with 30 parts by volume per minute of air using the pump 32, and cycled to the holding tank mentioned above.
  • the product syrup drawn off through the pipe 34 was exceptionally clear, containing only 25 ppm of suspended solids and having 70% transmission at 395 nm, so that only a polish filtration was required to give a fully clarified syrup.
  • the filter aid consumption amounted to no more than 0.07% calculated on the syrup when using a flow rate of about 70 litres per square foot per hour.
  • Scum from the clarifier was drained off through pipe 33 at about 80 parts by volume per minute. It contained 11.47% suspended solids comprising 37.5% protein, 40% oil and fats and 22.5% fibres, etc.
  • the syrup was then aerated by agitation and 0.5 ml of 0.1% TALOFLOTE A5 solution (about 5 ppm flocculant on syrup) was mixed in with non-turbulent agitation. Separation was then allowed to ensue for 5 minutes, giving a floated mud volume of about 10% and about 90% clear syrup.
  • 0.1% TALOFLOTE A5 solution about 5 ppm flocculant on syrup
  • the clarified syrup was very clear and contained less than 50 ppm of suspended solids.
  • the flocculant dose could be varied between 2.5 and 10 ppm when using 35 ppm Al, and when using 34 ppm Al the flocculant type could be varied between charge densities of 30 to 60% by weight acrylate.
  • the floated scum produced contained some glucose. An investigation was performed to see how much glucose was occluded in the scum and how much might be recovered by simple washing on a filter membrane.
  • the scum gave 200 ml 0.2wt% liquor. This represents 0.65% original glucose. Filtration was performed quite easily, without much 'blinding' of the filter cloth. Thus, some glucose was indeed present in the scum but could be recovered by washing, should economic and other factors be favourable.
  • Clarity (given by optical transmission at 393 nm) and calcium levels were then assessed as follows: As can be seen in the above results, clarification at pH 6.0 by the procedure based on a sucrose retention-flocculation clarification scheme has the following disadvantages:
  • the glucose syrup at 80°C was treated with 75% phosphoric acid (6 ppm P 2 0 5 on syrup), aluminium sulphate (A1 2 (S0 4 ) 3 16H 2 0) (26 ppm Al on syrup) and sodium hydroxide (100 ppm on syrup).
  • the sample was aerated and TALOFLOTE polyacrylamide flocculant (5 ppm on syrup) then added.
  • Impurities were allowed to separate by flotation. Clarified syrup was filtered through a course paper before analysis. Again for comparison purposes an aliquot of the original syrup was filtered using diatomaceous earth to produce a control sample of clean glucose syrup, representing the current factory process.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Organic Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Jellies, Jams, And Syrups (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Medicines Containing Plant Substances (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
EP81301807A 1980-05-02 1981-04-23 Reinigung hydrolysierter Stärke Expired EP0040473B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81301807T ATE2850T1 (de) 1980-05-02 1981-04-23 Reinigung hydrolysierter staerke.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8014798 1980-05-02
GB8014798 1980-05-02

Publications (2)

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EP0040473A1 true EP0040473A1 (de) 1981-11-25
EP0040473B1 EP0040473B1 (de) 1983-03-23

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EP81301807A Expired EP0040473B1 (de) 1980-05-02 1981-04-23 Reinigung hydrolysierter Stärke

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EP (1) EP0040473B1 (de)
JP (1) JPS56164800A (de)
AT (1) ATE2850T1 (de)
AU (1) AU537510B2 (de)
CA (1) CA1176245A (de)
DE (1) DE3160124D1 (de)
DK (1) DK154440C (de)
ES (1) ES501803A0 (de)
GB (1) GB2075510B (de)
GR (1) GR75244B (de)
IE (1) IE51198B1 (de)
MX (1) MX155779A (de)
ZA (1) ZA812828B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114292966A (zh) * 2021-12-23 2022-04-08 巴彦淖尔华恒生物科技有限公司 一种淀粉糖液中絮凝蛋白的分离方法及应用

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2136446B (en) * 1983-03-15 1986-09-17 Coca Cola Co Purification of sugar syrups
DE102008020429B4 (de) * 2008-04-24 2012-02-02 Südzucker AG Mannheim/Ochsenfurt Verfahren zur Elektroporation von Rübenschnitzeln und Vorrichtung zur Durchführung dieses Verfahrens

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE617706C (de) * 1931-09-06 1935-08-24 Carbo Norit Union Verwaltungs Verfahren zum Entfaerben und Klaeren von waessrigen Loesungen
GB1397927A (en) * 1971-06-22 1975-06-18 Tate & Lyle Ltd Separation of suspended solids from liquids

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE617706C (de) * 1931-09-06 1935-08-24 Carbo Norit Union Verwaltungs Verfahren zum Entfaerben und Klaeren von waessrigen Loesungen
GB1397927A (en) * 1971-06-22 1975-06-18 Tate & Lyle Ltd Separation of suspended solids from liquids

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114292966A (zh) * 2021-12-23 2022-04-08 巴彦淖尔华恒生物科技有限公司 一种淀粉糖液中絮凝蛋白的分离方法及应用

Also Published As

Publication number Publication date
GB2075510B (en) 1983-11-09
DK154440B (da) 1988-11-14
DK195681A (da) 1981-11-03
AU6990481A (en) 1981-11-05
EP0040473B1 (de) 1983-03-23
DK154440C (da) 1989-04-10
JPS6364199B2 (de) 1988-12-09
DE3160124D1 (en) 1983-04-28
ZA812828B (en) 1982-04-28
ATE2850T1 (de) 1983-04-15
JPS56164800A (en) 1981-12-17
IE51198B1 (en) 1986-10-29
ES8305831A1 (es) 1983-04-16
ES501803A0 (es) 1983-04-16
AU537510B2 (en) 1984-06-28
GR75244B (de) 1984-07-13
IE810930L (en) 1981-11-02
CA1176245A (en) 1984-10-16
MX155779A (es) 1988-04-28
GB2075510A (en) 1981-11-18

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