CN103537191A - Method for concentrating glucose by using membrane distillation - Google Patents
Method for concentrating glucose by using membrane distillation Download PDFInfo
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- CN103537191A CN103537191A CN201310507074.XA CN201310507074A CN103537191A CN 103537191 A CN103537191 A CN 103537191A CN 201310507074 A CN201310507074 A CN 201310507074A CN 103537191 A CN103537191 A CN 103537191A
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Abstract
The invention provides a method for concentrating glucose by using membrane distillation, relates to the field of glucose concentration, and solves the problem of an existing glucose concentration method that the energy consumption is high. The method comprises the following steps: 1 heating a glucose water solution; and 2 carrying out the membrane distillation and repeatedly concentrating until a crystal appears. According to the method, operation conditions are moderate, the heat lost in the process of an evaporation method can be reduced, the energy consumption in an evaporation and crystallization process is reduced, the glucose can be concentrated to be more than 50% and the water content of the glucose can be reduced to 30%-50%; the method is easy to operate automatically, is small in occupied area, is low in energy consumption and is easy to detach; residual heat of factories and solar energy can be used. The method is mainly used for concentrating the glucose.
Description
Technical field
The present invention relates to the concentrated field of glucose, relate to the method that adopts membrane distillation concentration glucose.
Background technology
Film distillation is a kind of new membrane isolation technics growing up in recent years.It utilizes hydrophobic microporous membrane that two kinds of different aqueous solution of temperature are separated, and under the poor effect of film both sides water vapour pressure, the steam of hot side enters cold side by fenestra, under cold side condensation.Condensation process is identical with evaporation---transmission---in conventional distillation for film distillation.Both take gas---liquid balance, as basis, all needs evaporation latent heat to realize phase transformation.Film still-process is compared with traditional separation process, has the following advantages: (1) film still-process is almost to carry out under normal pressure, and also there is the possibility of realization in the weaker area of simple, the easy to operate ， of equipment technical force; (2), in the film still-process of the Nonvolatile solute aqueous solution, because only have water vapour can see through fenestra, so distillate is very pure, be expected to become effective means extensive, that low cost is prepared ultra-pure water; (3) this process can be processed the aqueous solution of high concentration, if solute is the material of easy crystallization, solution can be concentrated to hypersaturated state and occurs film distillation crystalline polamer, and be current unique membrane process of crystallized product of directly isolating from solution; (4) film distillation assembly is easy to be designed to recovery of latent heat form, and has the flexibility that forms large-scale production system with efficient small-sized membrane module; (5) in this process without solution is heated to boiling point, as long as film both sides maintain the suitable temperature difference, this process just can be carried out, and likely utilizes the waste heat of solar energy, underground heat, hot spring, factory and the warm cheap energy such as industrial wastewater.At present, film distillation technology has application prospect in desalinization, ultra-pure water preparation, wastewater treatment and copolymer separation.And in theory, film distillation is a kind of unique method that can directly process the aqueous solution of high concentration, be undoubtedly a kind of method of condensed matter, in recent years, there is people progressively to attempt film distillation technology to be used in concentrated field.
Glucose is called again corn sugar, corn sugar, even referred to as glucose, is the widest and of paramount importance a kind of monose of distributed in nature, and it is a kind of polyhydroxy aldehyde.Pure glucose is clear crystal, and pleasantly sweet but sweet taste, should be water-soluble not as sucrose, is slightly soluble in ethanol, is insoluble to ether.Aqueous solution optically-active to the right, therefore also claim " dextrose ".Glucose has critical role in field of biology, is energy source and the metabolic intermediate product of living cells.Plant can produce glucose by photosynthesis.In candy manufacturing industry and field of medicaments extensive application.Gluconic acid series of products are the industry purposes such as food, medicine a kind of products very widely, in human body metabolism, play an important role, so American Pharmacopeia is loaded with calcium gluconate injection, tablet, K-IAO, the iron gluconate Deng Bing U.S. and produces in a large number.In the very flourishing Japan of food processing industry, on food additives certificate, clearly record gluconic acid, glucono-δ-lactone, zinc gluconate, calcium gluconae, ferrous gluconate, copper gluconate and can be used as food additives, take glucose as raw material deep processing, except manufacturing the gluconic acid, glucono-δ-lactone of crystallization, also can manufacture various salt, as potassium, sodium, calcium, magnesium, zinc, iron, copper etc.These are all the necessary trace elements of human body, human body lacks them, will there is disease, as iron deficiency will cause anaemia, because iron is the tissue part of hemoglobin and myoglobins, participate in oxidation and transport of carbon dioxide, past Ferrous Sulphate for Treatment anaemia, though human body can absorb, but stimulating gastrointestinal, can cause a series of bad reactions, therefore use instead after ferrous gluconate, stomach and intestine are without significant reaction, benefit iron is respond well, in light of this situation, national regulation, potassium with gluconic acid, sodium, calcium, zinc, copper, iron, manganese etc. are as human nutrition hardening agent and medicinal replenishers, all there is good result for the treatment of.
Industrial glucose is made by Starch Hydrolysis, the sixties using microbe Production by Enzymes glucose.This is a significant innovation, than acid-hydrolysis method, has obvious advantage.Raw material needn't be refined aborning, does not need acidproof, withstand voltage equipment, and liquid glucose is without bitter taste, and sugar yield is high.Yet glucose content is low in initial glucose syrup, water content higher (80% left and right), generally adopts evaporation technology to prepare crystal glucose.The power consumption of evaporation concentration technology is high, floor space large, produce a large amount of waste heats, is unfavorable for environmental protection.In this process, except the height that consumes energy, 1 ton of water of every evaporation also needs to consume 0.25～0.3 ton of steam, has wasted waste heat, develops new glucose concentration technology extremely urgent.
Summary of the invention
The object of the invention is, in order to solve the existing glucose method for concentration high problem that consumes energy, provides a kind of method that adopts membrane distillation concentration glucose.
The present invention adopts the method for membrane distillation concentration glucose, comprises following step:
One, by thermal source, D/W in head tank being heated to temperature is 30 ℃～80 ℃;
Two, after D/W temperature constant in head tank, material liquid, through the feed side of the membrane module of hydrophobic property, carries out film distillation, through repeatedly concentrated until there is crystallization, completes membrane distillation concentration glucose.
The present invention comprises following beneficial effect:
1, the present invention adopts in the method for membrane distillation concentration glucose because D/W can not infiltrate film, and moisture sees through film with steam form, in per-meate side generation condensation, and constantly circulation, thus reach concentrated object;
2, film distillation technology of the present invention is because operating condition is gentle, there is no need to add too much heat to equipment, can reduce the heat that method of evaporating loses during the course, reduce the energy consumption in evaporation and crystal process, due to film distillation technology, can utilize the clean energy resourcies such as upstream factory used heat waste heat, solar energy as thermal source, be a kind of novel concentration technology of clean environmental protection;
3, the present invention can concentrate glucose to concentration more than 50%, greatly reduce the water content of glucose, make glucose water content be reduced to 30%～50%, reduce energy consumption, and the concentrated glucose advantage of the film way of distillation is to be easy to automation mechanized operation, floor space is little, energy consumption is low, handling are simple and can utilize waste heat of plant.
Accompanying drawing explanation
Fig. 1 is the concentrated glucose solution flow chart of direct contact membrane distillation method and the absorption film way of distillation, and wherein 1 is heater, and 2 is storage tank, and 3 and 7 is centrifugal pump, and 4 is film distillation assembly, and 5,6,9 and 10 is valve, and 8 is condenser;
Fig. 2 is the concentrated glucose solution flow chart of vacuum membrane distillation method, and wherein 1 is heater, and 2 is storage tank, and 3 is centrifugal pump, and 4 is film distillation assembly, and 5 is condenser, and 6 is valve, and 7 is fluid reservoir, and 8 is surge tank, and 9 is vavuum pump;
Fig. 3 is the concentrated glucose solution flow chart of the gap membrane way of distillation, and wherein 1 is heater, and 2 is storage tank, and 3 and 7 is centrifugal pump, and 4 is film distillation assembly, and 5 is condenser, and 6,8,9 and 10 is valve, and 11 is fluid reservoir.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: a kind of method that adopts membrane distillation concentration glucose of present embodiment, carry out according to the following steps:
One, by thermal source, D/W in head tank being heated to temperature is 30 ℃～80 ℃;
Two, after D/W temperature constant in head tank, material liquid, through the feed side of the membrane module of hydrophobic property, carries out film distillation, through repeatedly concentrated until there is crystallization, completes membrane distillation concentration glucose.
The beneficial effect of present embodiment:
1, present embodiment adopts in the method for membrane distillation concentration glucose because D/W can not infiltrate film, and moisture sees through film with steam form, in per-meate side generation condensation, and constantly circulation, thus reach concentrated object;
2, present embodiment film distillation technology is because operating condition is gentle, there is no need to add too much heat to equipment, can reduce the heat that method of evaporating loses during the course, reduce the energy consumption in evaporation and crystal process, due to film distillation technology, can utilize the clean energy resourcies such as upstream factory used heat waste heat, solar energy as thermal source, be a kind of novel concentration technology of clean environmental protection;
3, present embodiment can concentrate glucose to concentration more than 50%, greatly reduce the water content of glucose, make glucose water content be reduced to 30%～50%, reduce energy consumption, and the concentrated glucose advantage of the film way of distillation is to be easy to automation mechanized operation, floor space is little, energy consumption is low, handling are simple and can utilize waste heat of plant.
The specific embodiment two: present embodiment is different from the specific embodiment one: described in step 1 D/W in head tank is heated to temperature be 50 ℃～60 ℃.Other is identical with the specific embodiment one.
The specific embodiment three: present embodiment is different from the specific embodiment one or two: the membrane module described in step 2 is plate type membrane assembly or doughnut formula membrane module.Other is identical with the specific embodiment one or two.
The specific embodiment four: present embodiment is different from one of specific embodiment one to three: the film of the hydrophobic property described in step 2 be hydrophobic microporous membrane, polyvinylidene fluoride dewatering film, hydrophobic polypropylene film or hydrophobically modified after hydrophobic film.Other is identical with one of specific embodiment one to three.
The specific embodiment five: present embodiment is different from one of specific embodiment one to four: the film distillation mode described in step 2 is direct contact membrane distillation, absorbing film distillation, vacuum membrane distillation or gap membrane distillation.Other is identical with one of specific embodiment one to four.
The specific embodiment six: present embodiment is different from one of specific embodiment one to five: described direct contact membrane distillation carries out according to following steps:
One, by thermal source, the D/W in head tank being heated to temperature is 50 ℃～80 ℃;
Two, after D/W temperature constant in head tank, the D/W of constant temperature is entered to direct contact type membrane module feed side through centrifugal pump, at the cold side of direct contact type membrane module, it is cold fluid and to keep temperature be under the condition of 0 ℃～30 ℃, through repeatedly concentrated until there is crystallization, complete membrane distillation concentration glucose; Wherein said cold fluid is water.
Other is identical with one of specific embodiment one to five.
The specific embodiment seven: present embodiment is different from one of specific embodiment one to six: described absorbing film distillation is carried out according to following steps:
One, by thermal source, the D/W in head tank being heated to temperature is 30 ℃～50 ℃;
Two, after D/W temperature constant in head tank, the raw material of constant temperature is entered to direct contact type membrane module feed side through centrifugal pump, at the cold side of direct contact type membrane module, it is cold fluid and to keep temperature be under the condition of 10 ℃～25 ℃, through repeatedly concentrated until there is crystallization, complete membrane distillation concentration glucose; Wherein cold fluid is that quality percentage composition is 20%～60% ease of solubility salting liquid, adds ease of solubility salting liquid guarantee that cold fluid concentration of salt solution is higher than glucose solution concentration by upstream valve.
Other is identical with one of specific embodiment one to six.
The specific embodiment eight: present embodiment is different from one of specific embodiment one to seven: the ease of solubility salt described in step 2 is sodium chloride, potassium chloride, sodium nitrate or carbonic hydroammonium.Other is identical with one of specific embodiment one to seven.
The specific embodiment nine: present embodiment is different from one of specific embodiment one to eight: described vacuum membrane distillation carries out according to following steps:
One, by thermal source, the D/W in head tank being heated to temperature is 50 ℃～80 ℃;
Two, after D/W temperature constant in head tank, the raw material of constant temperature is entered to direct contact type membrane module feed side through centrifugal pump, cold side at direct contact type membrane module is evacuated under the condition that vacuum is 0.1～3KPa, through repeatedly concentrated until there is crystallization, complete membrane distillation concentration glucose.
Other is identical with one of specific embodiment one to eight.
The specific embodiment ten: present embodiment is different from one of specific embodiment one to nine: described gap membrane distillation is carried out according to following steps:
One, by thermal source, the D/W in head tank being heated to temperature is 50 ℃～80 ℃;
Two, after D/W temperature constant in head tank, the raw material of constant temperature enters direct contact type membrane module feed side through centrifugal pump, at the cold fluid of direct contact type membrane module, through condenser, reduce cold drawing temperature and to cold drawing temperature be under the condition of-10 ℃～5 ℃, through repeatedly concentrated until there is crystallization, complete membrane distillation concentration glucose; Wherein cold fluid is that volumn concentration is 30%～70% glycol water.
Other is identical with one of specific embodiment one to nine.
Embodiment mono-:
The present embodiment adopts the method for membrane distillation concentration glucose, according to following steps, carries out:
Select hydrophobicity polyvinylidene fluoride microporous film as membrane material, select hollow fiber film assembly, the mode of film distillation is direct contact membrane distillation, and material liquid is glucose stoste (glucose quality percentage composition is 20%), cold fluid is the water of (0 ± 0.5) ℃, as shown in Figure 1, wherein 1 is heater to direct contact membrane distillation method flow chart, and 2 is storage tank, 3 and 7 is centrifugal pump, 4 is film distillation assembly, and 5,6,9 and 10 is valve, and 8 is condenser.
1 ton of material liquid is put into holding vessel, by thermal source, be heated to 70 ℃, valve-off 6, adopt pump that glucose solution is delivered to membrane module material liquid one side, open valve 10 simultaneously, valve 5 and valve 9, carry cold fluid to membrane module opposite side, on film surface, material liquid distills, steam condenses under condensate liquid effect, by water, taken out of system, through condenser, lower the temperature, keeping cooling fluid temperature is (0 ± 0.5) ℃, through repeatedly circulation, every 2 hours, open valve 6, sampling, observe fluid situations, analytical concentration, crystallization to be occurred, end operation, glucose solution is emitted.
Adopting flat effective film area is 20m
2, 2 membrane modules, operation 8h, it is 55% that glucose solution concentration is promoted to quality percentage composition, distills out moisture and is about 640kg.
Embodiment bis-:
The present embodiment adopts the method for membrane distillation concentration glucose, according to following steps, carries out:
Select hydrophobicity polyvinylidene fluoride microporous film as membrane material, select hollow fiber film assembly, the mode of film distillation is absorption film distillation, material liquid is glucose stoste (glucose quality percentage composition is 20%), the sodium chloride solution that the quality percentage composition that cold fluid is (12 ± 2) ℃ is 24%, absorption film way of distillation flow chart as shown in Figure 1, wherein 1 is heater, 2 is storage tank, 3 and 7 is centrifugal pump, 4 is film distillation assembly, 5, 6, 9 and 10 is valve, 8 is that (absorption distillation device is identical with direct contact membrane distillation device for condenser, compare with direct contact membrane distillation, this mode need not heat or heating-up temperature low, hot side temperature only needs 30 ℃～50 ℃).
1 ton of material liquid is put into holding vessel, thermal source is controlled feeding temperature and is controlled 50 ℃, valve-off 6, adopt pump that glucose solution is delivered to membrane module material liquid one side, open valve 10 simultaneously, valve 5 and valve 9(triple valve), make pipeline be connected state, the sodium chloride solution that conveying cold fluid quality percentage composition is 24% is to membrane module opposite side, on film surface, material liquid distills, steam sees through fenestra and runs into sodium chloride solution, after condensation, with sodium chloride solution, flow out system, through condenser, lower the temperature again, keeping cooling fluid temperature is (12 ± 2) ℃, repeatedly circulation, every 2 hours, open valve 6, sampling, observe fluid situations, analytical concentration, crystallization to be occurred, end operation, glucose solution is emitted.
Material liquid is put into holding vessel start to repeatedly circulation, crystallization to be occurred, in this process of end operation, need regularly at valve 9(, to be adjusted to threeway state) sampling, check concentration, when concentration is lower than 20%(quality percentage composition) time, then open upstream valve 10, add high concentration chlorination sodium solution or sodium chloride supersaturated solution, guarantee that valve 9 place's sampling concentration are higher than 20%(quality percentage composition).
Adopting flat effective film area is 20m
2, 2 membrane modules, operation 8h, it is 52% that glucose solution concentration is promoted to quality percentage composition, distills out moisture and is about 615kg.
Embodiment tri-:
The present embodiment adopts the method for membrane distillation concentration glucose, according to following steps, carries out:
Select hydrophobic polypropylene as microporous membrane material, select plate type membrane assembly, the mode of film distillation is vacuum membrane distillation, material liquid is glucose stoste (glucose quality percentage composition is 20%), and as shown in Figure 2, wherein 1 is heater to vacuum membrane distillation method flow chart, 2 is storage tank, 3 is centrifugal pump, and 4 is film distillation assembly, and 5 is condenser, 6 is valve, 7 is fluid reservoir, and 8 is surge tank, and 9 is vavuum pump.
1 ton of material liquid is put into holding vessel, and thermal source is heated to 60 ℃, valve-off 6, open pump transferring raw material, hot side realizes thermal cycle, and cold side vacuumizes, vacuum keep, at 0.3KPa, is opened condenser, and (due to permeable pressure head) steam is because vacuum is drawn out of system, at condenser, condense in place, flows in fluid reservoir, every 2h, open valve 6 detectable concentrations and fluid situations, analytical concentration, crystallization to be occurred, end operation, emits glucose solution.
Membrane module effective film area 15m
2, 2, operation 9h, it is 60.6% that raw glucose solution is concentrated into quality percentage composition, distills out and is about 670kg steam.
Embodiment tetra-:
The present embodiment adopts the method for membrane distillation concentration glucose, according to following steps, carries out:
Select hydrophobic polypropylene microporous barrier as membrane material, select hollow fiber film assembly, the mode of film distillation is gap membrane distillation, material liquid is glucose stoste (glucose quality percentage composition is 20%), in cold plate, pass into volumn concentration and be 45% glycol water as condensate liquid, guarantee that cold plate temperature is (10 ± 1) ℃, gap membrane way of distillation flow chart as shown in Figure 3, wherein 1 is heater, and 2 is storage tank, and 3 and 7 is centrifugal pump, 4 is film distillation assembly, 5 is condenser, and 6,8,9 and 10 is valve, and 11 is fluid reservoir.
1 ton of material liquid is put into holding vessel, by thermal source, be heated to 70 ℃, valve-off 6, adopt pump that glucose solution is delivered to membrane module material liquid one side, open valve 10 simultaneously, valve 8 and valve 9, carry cold fluid cold plate, steam goes out condensation at cold plate after film, flow out film, enter in storage tank 11, cold fluid glycol water circulates with pump, use condenser to control temperature, make glycol water temperature for (5 ± 1) ℃, repeatedly circulation, every 2 hours, open valve 6, sampling, observe fluid situations, analytical concentration, crystallization to be occurred, end operation, glucose solution is emitted.
Adopting flat effective film area is 20m
2, 2 membrane modules, operation 8h, it is 58% that glucose solution concentration is promoted to quality percentage composition, distills out moisture and is about 655kg, distilled water recoverable.
Certainly, above-mentioned explanation is not limitation of the present invention, and the present invention is also not limited only to number for example, and those skilled in the art of the present technique make variation, remodeling, add or replace and also belong to protection domain of the present invention in essential scope of the present invention.
Claims (10)
1. adopt a method for membrane distillation concentration glucose, it is characterized in that it carries out according to following steps:
One, by thermal source, D/W in head tank being heated to temperature is 30 ℃～80 ℃;
Two, after D/W temperature constant in head tank, material liquid, through the feed side of the membrane module of hydrophobic property, carries out film distillation, through repeatedly concentrated until there is crystallization, completes membrane distillation concentration glucose.
2. a kind of method that adopts membrane distillation concentration glucose according to claim 1, it is characterized in that described in step 1 D/W in head tank is heated to temperature be 50 ℃～60 ℃.
3. a kind of method that adopts membrane distillation concentration glucose according to claim 1, is characterized in that the membrane module described in step 2 is plate type membrane assembly or doughnut formula membrane module.
4. a kind of method that adopts membrane distillation concentration glucose according to claim 1, the film that it is characterized in that the hydrophobic property described in step 2 be hydrophobic microporous membrane, polyvinylidene fluoride dewatering film, hydrophobic polypropylene film or hydrophobically modified after hydrophobic film.
5. a kind of method that adopts membrane distillation concentration glucose according to claim 1, the film distillation mode described in step 2 that it is characterized in that is direct contact membrane distillation, absorbing film distillation, vacuum membrane distillation or gap membrane distillation.
6. a kind of method that adopts membrane distillation concentration glucose according to claim 5, is characterized in that described direct contact membrane distillation carries out according to following steps:
One, by thermal source, the D/W in head tank being heated to temperature is 50 ℃～80 ℃;
Two, after D/W temperature constant in head tank, the D/W of constant temperature is entered to direct contact type membrane module feed side through centrifugal pump, at the cold side of direct contact type membrane module, it is cold fluid and to keep temperature be under the condition of 0 ℃～30 ℃, through repeatedly concentrated until there is crystallization, complete membrane distillation concentration glucose; Wherein said cold fluid is water.
7. a kind of method that adopts membrane distillation concentration glucose according to claim 5, is characterized in that described absorbing film distillation carries out according to following steps:
One, by thermal source, the D/W in head tank being heated to temperature is 30 ℃～50 ℃;
Two, after D/W temperature constant in head tank, the raw material of constant temperature is entered to direct contact type membrane module feed side through centrifugal pump, at the cold side of direct contact type membrane module, it is cold fluid and to keep temperature be under the condition of 10 ℃～25 ℃, through repeatedly concentrated until there is crystallization, complete membrane distillation concentration glucose; Wherein cold fluid is that quality percentage composition is 20%～60% ease of solubility salting liquid, adds ease of solubility salting liquid guarantee that cold fluid concentration of salt solution is higher than glucose solution concentration by upstream valve.
8. a kind of method that adopts membrane distillation concentration glucose according to claim 7, is characterized in that the ease of solubility salt described in step 2 is sodium chloride, potassium chloride, sodium nitrate or carbonic hydroammonium.
9. a kind of method that adopts membrane distillation concentration glucose according to claim 5, is characterized in that described vacuum membrane distillation carries out according to following steps:
One, by thermal source, the D/W in head tank being heated to temperature is 50 ℃～80 ℃;
Two, after D/W temperature constant in head tank, the raw material of constant temperature is entered to direct contact type membrane module feed side through centrifugal pump, cold side at direct contact type membrane module is evacuated under the condition that vacuum is 0.1～3KPa, through repeatedly concentrated until there is crystallization, complete membrane distillation concentration glucose.
10. a kind of method that adopts membrane distillation concentration glucose according to claim 5, is characterized in that described gap membrane distillation carries out according to following steps:
One, by thermal source, the D/W in head tank being heated to temperature is 50 ℃～80 ℃;
Two, after D/W temperature constant in head tank, the raw material of constant temperature enters direct contact type membrane module feed side through centrifugal pump, at the cold fluid of direct contact type membrane module, through condenser, reduce cold drawing temperature and to cold drawing temperature be under the condition of-10 ℃～5 ℃, through repeatedly concentrated until there is crystallization, complete membrane distillation concentration glucose; Wherein cold fluid is that volumn concentration is 30%～70% glycol water.
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| WO2018018864A1 (en) * | 2016-07-27 | 2018-02-01 | 大唐环境产业集团股份有限公司 | Membrane distillation crystallization treatment device and method |
| CN109439807A (en) * | 2018-12-18 | 2019-03-08 | 浙江华康药业股份有限公司 | A kind of xylose production process |
| CN109673885A (en) * | 2019-01-07 | 2019-04-26 | 哈尔滨工业大学（威海） | A kind of method of full embrane method inspissated juice |
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| WO2018018864A1 (en) * | 2016-07-27 | 2018-02-01 | 大唐环境产业集团股份有限公司 | Membrane distillation crystallization treatment device and method |
| CN109439807A (en) * | 2018-12-18 | 2019-03-08 | 浙江华康药业股份有限公司 | A kind of xylose production process |
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Application publication date: 20140129 |