CN1224717C - Sugarcane sugaring process substituted sulphurous acid method - Google Patents

Abstract

The present invention provides a new composite auxiliary agent for replacing sulfur dioxide generated by the combustion of sulfur in the traditional sugarcane sugar production technology by a sulfurous acid method to implement the sulfitation, the clarification and the decolorization of sugarcane juice, and the bleaching and the decolorization of syrup in new technology for producing sugar, which is a compound of chitin or chitosan having the molecular weight of 5000 to 3, 000, 000. The composite auxiliary agent is added to a mixed juice box of sugarcane juice after preliming in the production line of a sugarcane sugar refinery and then is added to a sugar boiling tank for multiple times, and the clarifying, the sugar boiling, the honey extracting, the centrifuging, the sieving and the packaging of white granulated sugar are carried out by a conventional method. The content of residual sulfur of the white granulated sugar produced by the method can be controlled to be between 0 to 10 mg/kg and can achieve a better quality index than that of white granulated sugar produced by a carbonic acid method. The original production technological procedures and equipment only need simple variation, the operation is simple, and the production cost is not increased. In addition, the total recovery rate of sugar is enhanced by 0.5 to 1%.

Description

A kind of cane sugar manufacture technology that replaces sulfurous method

Technical field

The present invention relates to a kind of industrialization sucrose method for manufacturing sugar, particularly adopt new auxiliary agent to replace in traditional sugarcane sulfurous method sugar refining technology the sulfurous gas that produces with burning sulphur sugarcane juice is carried out the stove drying clarify and decolorize and syrup is carried out secondary stove drying bleaching, thereby produce low-sulfur or do not have the cane sugar manufacture novel method of sulphur white sugar.

Background technology

The cane sugar manufacture technology has the history of more than one thousand years so far from ancient lime method, the development of phosphoric acid lime method.At present in the world the cane sugar manufacture industrial production generally adopt sulfurous method, carbonatation process and three kinds of technologies of " two-step approach " (promptly producing raw sugar earlier again through refining production white sugar) are arranged, wherein China mostly adopts preceding two kinds of production technique, and American States such as Australia, Cuba, Brazil mainly use " two-step approach " technology.The White Sugar Quality that carbonatation process is produced is more excellent, and residual sulfur content is lower, and generally all in 10mg/kg, but because this method technology is complicated, and investment is big, production cost is than the sulfurous method height, and the filter mud that produces easily absorbs airborne CO2 and generates CaCO3; Knot can't utilize firmly, causes environmental pollution, and many experts think should not advocate popularization; Though technology is propagated its belief on a large scale in some countries, because of its investment is big, technical process is long, is difficult to be accepted by developing country's (comprising China) " two-step approach "; And present developing country is particularly Chinese and some Asian countries, adopt sugar refinery of sulfurous method sugar refining technology to account for more than 80% of whole cane sugar factory sums, because this sugar refining technology existing decades of above history, technical maturity, investment economizes, other quality index reach the level of carbonatation process substantially except that the product sulfur-bearing is higher, thus in cane sugar manufacture still in occupation of dominant position.The flavescence but its residual sulfur content height, product easily get damp is kept outside of the door by big-and-middle-sized food-drink enterprise gradually, and the market competitiveness descends day by day, and this has become the difficult problem in the cane sugar manufacture industry.For many years, many experts and scholars, the disadvantage that scientific research department and enterprise exist at sulfitation process craft, having dropped into a large amount of energy studies, develop the auxiliary agent that much is used for the sulfurous method sugaring, as be used to strengthen the cane juice clarification effect polyacrylamide, be used to improve not following tens kinds of multiple auxiliary scouring agent (as sucrose ester one class) of boiling sugared condition or the like, but all can't replace the decolorizing effect that stove drying reaches, can only in the sugaring process, help out.Units such as the Guangzhou sugar chemical research institute of research institution on China sucrose production glycosyl ground, Guangxi University, Guangxi light industry research institute are in recent years also in the cane sugar manufacture The Study on New Technology of being devoted to replace stove drying, but do not see the open report of succeeing and breaking through so far, more the precedent of in production reality, not using.

Summary of the invention

In order to improve the weak point of the product that sulfurous method for a long time produces, the inventor is through particularly decolouring to cane juice clarification to sugar refining technology and the technology of syrup bleaching being furtherd investigate, and with different auxiliary agents clarify, bleaching, Decolorant Test, found a kind of advanced technology, simple, do not increase the process of producing sugar of the replacement tradition sugarcane sulfurous method of production cost again, this novel process is exactly chitin or chitosan composite assistant method (KJ-1 method).

Technical scheme of the present invention is achieved in that

The technology of cane sugar manufacture of the present invention comprise to tearing of sugarcane raw material separate, the pre-ash of squeezing, sugarcane juice handles, feeds then mixed juice case, clarify, filter, boil sugar, purging, centrifugal, sieve, pack processing step such as white sugar, its main inventive point is: the clarify and decolorize of sugarcane juice and syrup bleaching process adopt the composite assistant of chitin or chitosan.Promptly the composite assistant with chitin or chitosan replaces the stove drying process.

The clarify and decolorize process of above-described sugarcane juice is in the mixed juice case that on the cane sugar factory production line composite assistant diluent of chitin of the present invention or chitosan and phosphoric acid is added simultaneously behind the pre-ash of sugarcane juice, the composite assistant add-on is 1-100mg/kg sugarcane juice (dry weight with chitin calculates), concentration of phosphoric acid is 300-400ppm in the sugarcane juice, sucrose system refining composite assistant diluent add-on be controlled at the 0.5-1.2 liter/minute between.Sulfurous method operation routinely then with adding the sugarcane juice heating of sucrose system refining composite assistant and adding milk of lime, is led to settling tank again, removes throw out, filters, and obtains clarifying sugarcane juice.

The technological process of above-described syrup bleaching and the similar process of cane juice clarification, imitate after syrup that evaporating pots extract out are put into boiling pan from five, when adding the crystallised sugar kind, by the method that adds other auxiliary agent usually, the composite assistant diluent that divides several times to add chitin of the present invention or chitosan, every cubic metre of syrup of addition are 0.5g-20g (dry weight with chitin calculates), and boil sugar, purging according to a conventional method, centrifugal, sieve, obtain the white sugar product.

The composite assistant of chitin recited above or chitosan is the chitin of molecular weight 5000 to 3,000,000 or the mixture of chitosan, it is between 10,000 to 1,000,000 that best scheme is to use the molecular weight at cane juice clarification process chitin or chitosan, use is between 50,000 to 3,000,000 at the chitin of syrup bleaching or the molecular weight of chitosan, this sucrose system refining composite assistant is except clarifying, boil add in the sugar stage outside, also can be in squeezing, add in the operations such as purging, after using this chitin composite assistant, no longer need to adopt stove drying technology, also no longer need to add polyacrylamide, additives such as sucrose ester, clarification, boil sugar, purging, crystalline operational condition and technology do not change, but the white sugar quality product that obtains improves a lot, sulphur content can be reduced to minimum degree, also can not produce and get damp, phenomenons such as caking.

This chitin or chitosan are to adopt physics method or chemical method, biological process processing to obtain on the crust of animal, and these methods can be recognized in disclosed scientific and technical literature.As chemical method be with animal shell (preferred marine animal crust) earlier with the diluted acid decalcification, use the diluted alkaline deproteinated again, decolouring with organic solvent then obtains chitin; Chitin obtains chitosan with high temperature and concentrated base deacetylate again.Biological process is the crust of marine animal to be resolved into molecular weight with microorganism (enzyme that chitoanase, papoid, N,O-Diacetylmuramidase, genus bacillus produce etc.) reach 10,000 to several ten thousand chitin or chitosan, low-molecular-weight chitin or chitosan are applicable to squeezing or the cane juice clarification stage that temperature is lower, and high-molecular weight chitin or chitosan are applicable to higher the boiling sugar, purging stage of temperature.With chitin or chitosan 50-80 ℃ dilute acetic acid or diluted hydrochloric acid dissolution, join in settling pond or the boiling pan by the method that adds sucrose system refining composite assistant then before using.

Above-described chitin or chitosan are the mixtures that dissolves in faintly acid tunicin and polysaccharide, chitin claims chitin again, chitosan also claims chitosan, molecular formula is (C6H1104N) n, this kind high-molecular biologic preparation is the cationic edibility Mierocrystalline cellulose of finding in the world at present of unique positively charged (polyose), has good adsorptivity, selectivity and throwing out, also have very strong decolorization and freshening effect simultaneously, human body also had good health-care effect, be the main raw material(s) that is in fashion the multiple functional health-care food in the world at present, American-European-Japanese scientists calls isolating protein in the human body to its reputation, fat, carbohydrate, VITAMIN, the 6th vital principle that mineral substance is outer.The existing research report that is applied to aspects such as juice clarification, sewage disposal of domestic and international many scientific and technical literatures.Be applied in the cane sugar manufacture to replace stove drying to decolour clarification and boil any report of sugared viscosity reduction decolouring of sugarcane juice but still find no.

Compared with the prior art, outstanding substantive distinguishing features of the present invention and obvious improvement are:

Seek a kind of advanced technology, simple, do not increase the process of producing sugar of the replacement tradition sugarcane sulfurous method of production cost again, the inventor is in the past few years to the decolouring of the chitin or the chitosan of different molecular weight section, clarification, cohesion and viscosity-reducing mechanism carry out research trial, filter out with the chitin or the chitosan proportioning of one group of different molecular weight section and prepare the sucrose system refining composite assistant that can replace sugarcane sulfurous method sugar refining technology stove drying effect, and through laboratory lab scale and production actual tests, successfully be applied in the cane sugar manufacture scale operation, created a kind of cane sugar manufacture novel process of brand-new replacement sulfurous method.This novel technique advanced person does not need former sulfurous method production line is carried out too much transformation, and is easy and simple to handle, reduce investment outlay, do not increase production cost, just can produce low-sulfur even not have the high quality white granulated sugar of sulphur, and can improve about 0.5～1 percentage point of sugar total yield.Because the defining principle to the processing method title in the cane sugar manufacture technology is named by the decolouring finings that its clarification process adopts, cane sugar manufacture novel process of the present invention is intended called after " KJ-1 method cane sugar manufacture technology ".

The composite assistant sucrose system refining auxiliary agent of using chitin or chitosan replaces stove drying and carries out the theory that sugarcane juice decolouring, clarification and the mechanism of action of syrup viscosity reduction decolouring relate to relevant subjects such as cane sugar manufacture technology, organic chemistry, polymer science, solution, crystallization theory, colloidal theory, molecular motion and ionic potential.The mechanism of action of the composite assistant of chitin or chitosan in the cane juice clarification process is that the positively charged ion of its positively charged can adsorb electronegative inorganic non-sugar negatively charged ion and heavy metal salt ion in the sugarcane juice, quicken its formation precipitation of reuniting, simultaneously can also destroy non-sucrose and divide the colloidal electric double layer, make it reach isopotential point (being coacervation point alleged in the sugar refining technology), impel its coagulative precipitation.Free H+ ion and hydroxyl (CH2OH) in the composite assistant of chitin or chitosan has very strong decolorization simultaneously, can in clarifying process, reduce the colour of mixing sugarcane juice, make sugarcane juice needn't can reach the colour of sugar refining technology requirement through stove drying, thereby can replace the stove drying operation of old technology, thereby improve the quality of subsider juice, reach the purpose of producing low-sulfur or not having the sulphur white sugar.

The coloring matter that occurs in the sugaring process has original pigment of sugarcane such as chlorophyll, the sugarcane flavine, carotene and cyanin etc., these pigments only can be removed its part through cohesion and stove drying in traditional sugar refining technology, remaining part will be brought in the liquid glucose, many colorless substances of sugarcane juice combine with other compounds in the production process after clarification simultaneously, can generate coloring matter again after chemical combination or the decomposition, mainly contain phenols and aminocompound, and this two portions coloring matter mostly is electronegative material, so the KJ-1 of positively charged has stronger adsorption to them, the mechanism of KJ-1 decolorization that Here it is also is its reason that can replace stove drying in sucrose system sweetening process.

In sugar boiling process, because the composite assistant of chitin of the present invention or chitosan has very strong adsorptivity, can adsorb electronegative organic impurity in the syrup, simultaneously since its carbonium potential point equate substantially with colloidalmaterial in the syrup, event can be degraded the colloidalmaterial of syrup medium-high viscosity and be made syrup viscosity reduction in the sugar boiling process, increase its flowability, thereby improve the sugared condition of boiling, shorten and boil the sugar time.

Simultaneously, because the composite assistant of chitin or chitosan has the freshening effect that suppresses harmful enzyme bacteria growing, can prevent that to boiling sucrose decomposition and reducing sugar from generating in cane juice clarification, evaporation concentration in the whole system refining process of sugar honey, thereby can improve clear juice and syrupy simple purity, can make the sugar total yield improve 0.5～1%.

The white sugar that adopts the inventive method to produce, its residual sulphur content can be controlled between 0～10mg/kg, reaches even be better than the quality index of carbonatation process white sugar, and original production process flow process and equipment need only be done simple change, and is easy and simple to handle, do not increase production cost.

Other substantive distinguishing features of the present invention also is, the nutritive ingredient of sugarcane filter mud improves greatly, because it is a kind of organism useful to animals and plants that chitosan itself has, low-molecular-weight chitosan can be used as plant-growth regulator, animal-feed, also can be used as foodstuff additive, according to inventor's result of experiment, the composite assistant that adopts chitin of the present invention or chitosan is after the cane juice clarification operation is used, the time of the filter mud heap fermentation that filters out shortens greatly, fertilizer efficiency is more far better than sulfurous method, and carbonatation process can't be compared especially.

Description of drawings

Fig. 1 is the chemical method industrialized producing technology schema of the composite assistant of chitin of the present invention or chitosan.

Fig. 2 replaces the process flow sheet that sulfurous method sugar refining technology stove drying operation is produced low-sulfur, no sulphur white sugar for the composite assistant that the present invention uses chitin or chitosan.

Recognize that from Fig. 1 the composite assistant of chitin or chitosan is that animal shells such as shrimp crab are cleaned with clear water, immersion again adds dilute alkali, deproteinated, washing uses the diluted acid rinsing clean then again, with acetone or potassium permanganate decolouring, washing obtains molecular weight and is about 500,000 to 3,000,000 chitin; If chitin was further boiled 1-2 hour with the sodium hydroxide of 30-50% again, clean after drying, promptly obtain molecular weight and be about chitosan between 50,000 to 1,000,000, molecular weight is smaller if desired, can prolong the soda boiling time.

From Fig. 2, recognize, after the raw material sugarcane enters shredding machine, squeeze through squeezing machine, bagasse is sent to papermaking or is fully utilized, sugarcane juice adds a small amount of lime and carries out pre-ash processing, feed mixed juice case then, the composite assistant that adds phosphoric acid and chitin of the present invention or chitosan by normal amount, thorough mixing and heating back add an amount of milk of lime (main ash) by normal amount, deliver to settling tank again, throw out leaches filter mud with the vacuum drum filter, and clear juice filters with slanted screen and obtains clarifying clear juice, carry out quadruple effect or five and imitate evaporation, feed boiling pan, add crystallization in motion agent and sucrose system of the present invention refining composite assistant, technology and operational condition are boiled sugar routinely, purging again, sieve, obtain white sugar, packing.

Embodiment

Embodiment one

Get first after the coarse filtration of sugar refinery and squeeze the juice 500 milliliters, the phosphoric acid that adds the 400ppm/ amount of liter, shake stirring, pH value is controlled between the 4.2-5.8, press the 5-10ppm/g amount at every turn respectively and add KJ-1 auxiliary agent (dry weight with chitin calculates), the molecular weight of chitin or chitosan is between 10,000 to 1,000,000, add milk of lime again and carry out pre-ash, pH value is controlled between the 6.0-6.8, be heated to 50-60 ℃, add milk of lime again and lead ash, pH value is controlled between the 6.4-7.2, be heated to 100 ℃ then, pour sugarcane juice into graduated cylinder and put into 40-50 ℃ warm water and adopt the gradient cooling method to carry out sedimentation.This test is carried out 15 times altogether, and prepared clear juice chemical examination back major part reaches the sugar refining technology index request.

Embodiment two

Get 500 milliliters of mixing juices behind the pre-ash of sugarcane from sugar refinery at every turn and be preheated to 40-50 ℃, the KJ-1 auxiliary agent (dry weight with chitin calculates) that adds the 5-10ppm/ amount of liter, the molecular weight of chitin or chitosan is between 10,000 to 1,000,000, stir post-heating to 50-60 ℃, add milk of lime again to the PH6.4-7.2, shake up, be heated to 100 ℃, mixed juice after will boiling is poured graduated cylinder into, puts into 40-50 ℃ of warm water and adopts the gradient cooling method to carry out sedimentation, extracts clear juice chemical examination.This test is carried out five times altogether, does not wherein once add the KJ-1 auxiliary agent.The clear juice that 4 tests of assay result except that not adding KJ-1 are produced is all qualified.

Embodiment three

The triose that is numbered 336# on the production line of sugar refinery boils to divide in jar (28M3) and adds the KJ-1 chitin of 23kg or the composite assistant diluent (amount of solid is 200g) of chitosan 9 times, the molecular weight of chitin or chitosan is between 50,000 to 3,000,000, add for the first time 3kg, each later on 2.5kg that adds all adds water 10-15kg dilution at every turn.It is 7 hours that test-results is always boiled the sugar time, total consuming time 2 hours 40 minutes of sieve sugar is with not only the adding KJ-1 but also add two jars of 333#, the 334# of sucrose fat auxiliary scouring agent and only add the sugar time of boiling and the sieve sugar time that 335#, 337#, 338#, each jar of 339# of the composite assistant of chitin or chitosan consumed and all will lack of simultaneous test.Test effect is good.

Embodiment four

In the mixed juice case after on pressing 500 tons cane sugar factory production line day, the composite assistant diluent of KJ-1 chitin or chitosan and phosphoric acid being added the pre-ash of sugarcane juice simultaneously, the KJ-1 extension rate is that 200-500 is doubly to KJ-1 amount of solid ratio, the phosphoric acid add-on is controlled at 300-400ppm/ and rises between the sugarcane juice, KJ-1 auxiliary agent diluent add-on be controlled at the 0.5-1.2 liter/minute between.After 1 hour the flashboard on the SO2 stove drying pipeline is turned down 1/2, observe clarification settling tank each layer color value of clear juice and transparency, phenomenon does not note abnormalities; Again the flashboard on the SO2 stove drying pipeline is turned down 1/3 again after 2 hours, clarify still normally, clear juice sample examination is qualified, and the filtered juice amount increases, and strainability is good, and filter mud is more dried; Again the flashboard Close All on the stove drying pipeline, stop to clarify sulphuring after 3 hours, realized no sulphur clarification.Test was this time carried out 24 hours altogether, wherein clarified operation and all stopped sulphur about 20 hours.The clear juice of duration of test is total to sample examination 16 times, and wherein 6 (3#-8#) laboratory analysis of data contrast with preceding 6 the clear juice samples of traditional stove drying technology that adopt of test, and test effect is good.Add that the average color of clear juice is 70.67 (IU) behind the KJ-1, than not adding average color 72.5 before the KJ-1 auxiliary agent 1.83 (IU) that descend; Add that pH value mean value is 7.3 behind the KJ-1, than not adding 6.55 high by 0.75 before the KJ-1; The average hammer degree of clear juice is 17.47 ° of BX behind the interpolation KJ-1, than not adding the preceding high 1.59 ° of BX of 15.88 ° of BX of average hammer degree of KJ-1, wherein maximum and Schwellenwert differ 2.68 ° of BX, this explanation add clear juice behind the KJ-1 always contain sugar than before adding KJ-1 clearly the sugar that always contains of juice do not increase; The clear average simple purity of juice is 87.13% (AP) behind the interpolation KJ-1, the preceding average simple purity 84.31% (AP) of KJ-1 is not high 2.82 percentage points than adding, wherein maximum and Schwellenwert differ 6.19 percentage points, this has illustrated that adding behind the KJ-1 sucrose in the clear juice divides and increased, proof KJ-1 can prevent the decomposition that sucrose divides, and reduces the generation of reducing sugar.Show that from clear juice hammer degree and two index comparative analyses of simple purity the KJ-1 additive is significant to improving the effect of clear juice sugar degree.

Index comparative analyses such as syrup colour, hammer degree, simple purity prove that also the every index major part of syrup behind the interpolation KJ-1 is better than not adding the syrup index of KJ-1 before and after the composite assistant that adds chitin or chitosan, and this further proves the sugared effect of increasing of KJ-1.

From the white sugar sampling analysis result to 8 numberings of producing behind the composite assistant that adds chitin or chitosan, except that 2 numberings being arranged because colour exceeds standard for the secondary sugar, the white sugar of all the other 6 numberings reaches the first sugar standard.And wherein sulphur content the highest only be 8.4mg/kg, all reach sulphur content (20mg/kg following) index of carbon method white sugar, and Schwellenwert only is 6.0mg/kg, can match in excellence or beauty with the whole nation top-quality carbon method white sugar sulfur-bearing index fully.

Embodiment five (the composite assistant chemical method production example of chitin of the present invention or chitosan)

With clean sheet chitin raw material, earlier with in the alkaline solution that drops into 10-20%, reacted 3 hours, pull out and wash with water, add 10% dilute hydrochloric acid again and soak after-filtration, be washed to neutrality,, be put in the aqueous sodium hydroxide solution of 30-50% reaction again 3 hours with the potassium permanganate decolouring, dry the white plates chitosan, its deacetylation is 80-95%; (2), carboxylation reaction: above-mentioned sheet chitosan is placed organic solvent, adds acetate, stir, be heated to 40-60 ℃, reaction times 2-6 hour, filter, wash sheet acylation chitosan (molecular weight is 1-100 ten thousand);

Embodiment six (the composite assistant microbial method production example of chitin of the present invention or chitosan)

(1), with in the alkaline solution that drops into 10-20%, reacted 3 hours earlier with clean sheet chitin raw material, pull out and wash with water, add 10% dilute hydrochloric acid again and soak after-filtration, be washed to neutrality, decolour with potassium permanganate, obtain chitin, obtained chitosan in 2-3 hour with the 30-50% soda boiling then; (2) can produce in the thalline adding culture medium solution of chitoanase or bacterial classifications such as N,O-Diacetylmuramidase, genus bacillus, under 20-30 ℃, cultivate 48 hours, must produce the expansion bacterial classification; (3) will produce the expansion bacterial classification and be put in the fermentor tank, add chitosan and suitable quantity of water, under 20-30 ℃, cultivate 24-48 hour,, make the low-molecular-weight chitosan of 5000-50 ten thousand through sterilization.

Table 1: KJ-1 finings comparison of test results table is added in triose, methose purging (sieve sugar)

Table 2: add the KJ-1 finings and boil triose comparison of test results table

Claims (2)

1, a kind of cane sugar manufacture technology that replaces sulfurous method, comprise tearing of sugarcane raw material separated, squeezing, the pre-ash of sugarcane juice is handled, feed mixed juice case then, clarification, filter, boil sugar, purging, centrifugal, sieve, the step of packing white sugar, it is characterized in that: the process of the clarify and decolorize of sugarcane juice is in the mixed juice case that on the cane sugar factory production line composite assistant diluent of chitin or chitosan and phosphoric acid is added simultaneously behind the pre-ash of sugarcane juice, calculate with dry weight, composite assistant add-on: 1-100mg/kg sugarcane juice, the molecular weight of the composite assistant of chitin or chitosan is between 10,000 to 1,000,000, concentration of phosphoric acid is 300-400ppm in the sugarcane juice, composite assistant diluent add-on be controlled at the 0.5-1.2 liter/minute between, sulfurous method operation routinely then, the sugarcane juice heating of the composite assistant of chitin or chitosan will be added, and add milk of lime, lead to settling tank again, remove throw out, filter, obtain clarifying sugarcane juice; After syrup bleaching process is that five syrup of imitating the evaporating pot extraction are put into boiling pan, when adding the crystallised sugar kind, by the method that adds other auxiliary agent usually, divide several times to add the composite assistant diluent of chitin or chitosan, dry weight with chitin calculates, the every cubic metre of syrup of amount that adds chitin is 0.5g-20g, the molecular weight of the composite assistant of chitin or chitosan is between 50,000 to 3,000,000, boil sugar, purging more according to a conventional method, centrifugal, sieve, obtain the white sugar product.

2, the cane sugar manufacture technology of replacement sulfurous method according to claim 1 is characterized in that: the chitin of the composite assistant of said chitin or chitosan or chitosan are to adopt physics method or chemical method, biological process processing to obtain on the crust of animal.

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