CN1280988A - Equipment and process for preparing chitin polyose - Google Patents
Equipment and process for preparing chitin polyose Download PDFInfo
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- CN1280988A CN1280988A CN 99109831 CN99109831A CN1280988A CN 1280988 A CN1280988 A CN 1280988A CN 99109831 CN99109831 CN 99109831 CN 99109831 A CN99109831 A CN 99109831A CN 1280988 A CN1280988 A CN 1280988A
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Abstract
A chitin polyose is prepared form chitin and clkali solution in weight ratio of 1:(2-20) through feeding them in the first stage of multi-stage microwave fluidized bed and obtaining the chitin polyose from the output in last stage. Said alkali solution has a 30-60% concentration and is at 60-160 deg.c of temp. in the reaction process. Its equipment is composed of microwave fluidized bed, microwave cavity, thermometer, baffle and fluid distributor, material discharge valve, and material feed and discharge tubes. Its advantages include high quality and productivity of product, low energy consumption and no wastes discharge.
Description
The invention belongs to biological chemical field, particularly the equipment and the technology thereof of preparation chitosan.
The chitinous acetyl process of taking off is to prepare the important stage in the chitosan main-process stream by shrimp, crab shell; generally it be with chitin with 40%～50% sodium hydroxide under 80 ℃～150 ℃ condition through 10～20 hours reaction; make insoluble chitin take off the chitosan that ethanoyl becomes solubility; this chitinous deacetylation reaction needed highly basic high temperature reacts for a long time; the production intensity of equipment is very low, and how accelerating this reaction is the problem of multinational scientific and technological circle research.As far back as the seventies in this century, just find that micro-wave energy accelerates this reaction, for example 79 years United States Patent (USP)s 4159932 have just been reported the small-scale test of accelerating deacetylation with microwave, each chitin of handling is 15 grams, sodium hydroxide solution with 50% is used usual method, 100 ℃, 18 hours, reaction product was solvable with 2% acetic acid; Same condition is put into 120 ℃ of microwave ovens with sample, reaction in 15 minutes, and product is solvable too with 2% acetic acid, and the shortcoming of this test is not survey deacetylation, so can not quantitative comparison, but has illustrated that micro-wave energy accelerates the carrying out of this reaction.The people such as Yan Baifen of 95 years Shanghai Aquatic Products Univ. 9CN) have also carried out the test of microwave quickening deacetylation; their result of test is under the identical situation of other conditions; alkali concn 45%; 100 ℃ of temperature; 80 minutes time; deacetylation at microwave oven internal reaction sample is 86%, and the deacetylation of popular response sample is 62%, further illustrates the reaction that micro-wave energy is accelerated deacetylation.
More than test all is to carry out in an airtight microwave oven; how with this reaction; be applied to industrial production; very big difficulty is arranged: at first the degree of depth of microwave radiation has certain limit; for the equipment of one 0.5 rice diameter, present microwave also difficulty is radiated the center, in addition to an open system; how is the energy efficiency of microwave? also not seeing has report, does not see the expanding test that the microwave deacetylation is arranged and the report of production.
The object of the present invention is to provide a kind of equipment and technology thereof for preparing chitosan, adopt the microwave fluidized-bed reactor, material is reacted in an airtight container continuously, can not only make full use of the energy of microwave, and can realize the industrial production of microwave deacetylation.
The present invention is that raw material carries out deacetylation continuously with the chitin in the microwave fluidized-bed, at first prepare the alkaline solution of weight percent concentration 30～60%, be made into the slurry of 1: 2 to 1: 20 solid-to-liquid ratio by chitin and alkaline solution weight, join in the first step microwave fluidized-bed by feed-pipe then, after material is full, flow into the feed-pipe of microwave fluidized-bed bottom, the second stage by the carrier pipe of first step microwave fluidized-bed, enter in the microwave fluidized-bed of the second stage, after material is full, carrier pipe by second stage microwave fluidized-bed flow in the next stage microwave fluidized-bed, by that analogy, till when to the last the drainage conduit of one-level microwave fluidized-bed has slurries to flow out, make the solution of chitosan.The weight percent concentration of alkali is 30%～60% in the reaction process, and the optimum weight percentage concentration is 40～50%, regulates microwave power, and making temperature of reaction is 60 ℃～160 ℃, and the best is 90 ℃～120 ℃.
The chitosan slurry that the present invention discharges carries out suction filtration with the vacuum filtration machine, chitosan is separated with mother liquor, solid materials (wet cake) is a chitosan, mother liquor turns back to preparation alkaline solution operation deallocation material again, this mother liquor uses to a certain degree, reduce temperature, with the method for condensation-crystallization, sodium-acetate crystallization from the sodium acetate soln of degree of supersaturation is separated out, after the sodium-acetate that solution and crystallization are separated out separates with suction method, reclaim the by product sodium-acetate, at this moment mother liquor still returns the use of preparation alkaline solution operation, and sodium-acetate is washed several times with suction method, because of containing a large amount of alkali in the water lotion, still return use, become byproduct after the sodium-acetate drying.
The present invention utilizes microwave field energy penetrating material to accelerate the conversion of energy, thereby accelerates chemical reaction rate, and utilizes the relative movement of microwave fluidized bed fortification system solid-liquid and quickening velocity of diffusion to combine, so accelerated the deacetylation reaction process greatly.
In reaction process,, regulate the microwave power control reaction temperature, multistage microwave fluidized bed such as the the the the 4th, the 5th, the 6th, the 7th, the 8th, the 9th grade can be set according to required result by the thermometer thermometric.Give the fixed average left alone without help time of staying when reaching, determine the flow of slurry, at this moment enter stable operational stage, sampling is at regular intervals surveyed and is taken off the acetyl rate, after stable operation, take off acetyl rate to 85%, stopped reaction, product at this moment reaches the requirement of protective foods level.If the progression of microwave fluidized bed increases, the reaction times lengthening takes off the acetyl rate and is increased to 99%, and product at this moment reaches the leading indicator as medical material.
The washing of chitosan wet cake is to adopt the circulation WATER-WASHING METHOD, reaction density according to sodium hydroxide, and every batch of institute's water consumption, the washing 5～10 times that generally will circulate makes for the first time in the washing lotion concentration sodium hydroxide high as far as possible, and the alkali lye when being concentrated to 30%～60%NaOH also turns back to the front batching and uses like this, the operation power consumption is low like this, making does not have waste residue, discharge of wastewater in the flow process of the present invention, the consumption of not only having saved alkali has widely also greatly improved the pollution to environment.
The structure of microwave fluidized-bed of the present invention is: in the outside of microwave fluidized-bed 5 microwave cavity 3 is arranged, a thermometer 6 is arranged at top, there are carrier pipe 7 or drainage conduit 8 (in the end one-level claims drainage conduit) in the side on top, there are baffle plate 4 and fluid distributor 9 in inside, one blow-off valve 1 is arranged at the bed bottom in cone, and there is feed-pipe 2 side of bottom.
Device of the present invention is multistage microwave fluidized bed.The carrier pipe (last bed at multistage microwave fluidized-bed claims drainage conduit) and the feed-pipe of second stage microwave fluidized-bed lower side by first step upper side link, and the like, requirement according to technology constitutes multistage fluidized bed, its objective is in order to reduce back-mixing and the short circuit of material in reaction process, in large-scale production plant from now on, also can adopt level Four, Pyatyi ... Deng multilevel device, more help reaction process, save electric energy in a large number.Micro-wave energy is mainly used in the quickening chemical reaction, makes operating process more reasonable.
The present invention and traditional technology relatively have the following advantages: (to handle 1 ton of chitin)
Advantage of the present invention: (to handle 1 ton of chitin)
1. device fabrication strength ratio traditional method improves 80 times;
2. alkaline consumption reduces by 90%;
3. by-product recovery;
4. non-pollutant discharge;
5. take off the acetyl rate and can reach 99%.
Below in conjunction with accompanying drawing technical scheme of the present invention is further described.
Fig. 1: microwave fluidized-bed reactor synoptic diagram of the present invention;
Fig. 2: the multistage microwave fluidized-bed reactor of the present invention connects synoptic diagram.
Label in the accompanying drawing:
1. blow-off valve 2. feed-pipes 3. microwave cavities 4. baffle plates 5. microwave fluidized-beds
6. thermometer 7. carrier pipes 8. drainage conduit 9. fluid distributors
Embodiment 1.
Adopt three grades of microwave fluidized-bed reactors.Chitin with 1 kilogram, concentration is 40% NaOH10 kilogram, be made into the solid-to-liquid ratio slurry, feed-pipe 2 by microwave fluidized-bed reactor 5, crossing fluid distributor 9 joins in the first step microwave fluidized-bed reactor 5, enter into the feed-pipe 2 of next stage microwave fluidized-bed reactor 5 by baffle plate 4 by carrier pipe 7, with this, when the drainage conduit 8 of third stage microwave fluidized-bed reactor 5 has slurries to flow out till.Carry out suction filtration with the vacuum filtration machine, chitosan is separated with mother liquor, obtain the chitosan wet cake, mother liquor turns back to front deallocation material again, this mother liquor uses to a certain degree, reduce temperature,, sodium-acetate crystallization from the sodium acetate soln of degree of supersaturation is separated out with the method for condensation-crystallization, the sodium-acetate crystallization is separated out with after mother liquor separates with suction method, reclaim the by product sodium-acetate, at this moment mother liquor is returned the front again and use, sodium-acetate still with the suction method washing several times, because of containing a large amount of alkali in the water lotion, still return use, become byproduct after the sodium-acetate drying, the leftover materials after reaction is finished are discharged by blow-off valve 1.By thermometer 6 thermometrics, the adjusting microwave power is 1KW, gives the microwave fluidized-bed reactor 5 heating by microwave cavity 3, and the temperature of reaction process is 110 ℃, and the mean residence time that reacts whole process is 30 minutes, and taking off the acetyl rate is 90%.Embodiment 2.
Adopt three grades of microwave fluidized-bed reactors.1 kilogram of chitin, concentration are 30% NaOH20 kilogram, are made into the solid-to-liquid ratio slurry, and reaction process is with embodiment 1,90 ℃ of temperature of reaction, and mean residence time 90 minutes is made chitosan, takes off acetyl rate 95%.Embodiment 3.
Adopt three grades of microwave fluidized-bed reactors.1 kilogram of chitin, concentration are 45% NaOH15 kilogram, are made into the solid-to-liquid ratio slurry, and reaction process is with embodiment 1,140 ℃ of temperature of reaction, and mean residence time 15 minutes is made chitosan, takes off acetyl rate 92%.Embodiment 4.
Adopt nine grades of microwave fluidized-bed reactors.1 kilogram of chitin, concentration are 55% NaOH8 kilogram, are made into the solid-to-liquid ratio slurry, and reaction process is with embodiment 1,100 ℃ of temperature of reaction, and mean residence time 60 minutes is made chitosan, takes off acetyl rate 99%.
Claims (4)
1. equipment for preparing chitosan, it is characterized in that: microwave cavity (3) is arranged in the outside of microwave fluidized-bed (5), a thermometer (6) is arranged at top, there are carrier pipe (7) or drainage conduit (8) in the side on top, there are baffle plate (4) and fluid distributor (9) in inside, one blow-off valve (1) is arranged at the bed bottom in cone, and there is feed-pipe (2) side of bottom.
2. a kind of technology of utilizing the equipment for preparing chitosan to prepare chitosan as claimed in claim 1, it is characterized in that: the alkaline solution of at first preparing weight percent concentration 30～60%, be made into the slurry of 1: 2 to 1: 20 solid-to-liquid ratio by chitin and alkaline solution weight, join in the first step microwave fluidized-bed by feed-pipe then, after material is full, flow into the feed-pipe of microwave fluidized-bed bottom, the second stage by the carrier pipe of first step microwave fluidized-bed, enter in the microwave fluidized-bed of the second stage, after material is full, carrier pipe by second stage microwave fluidized-bed flow in the next stage microwave fluidized-bed, by that analogy, till when to the last the drainage conduit of one-level microwave fluidized-bed has slurries to flow out, make the solution of chitosan, regulate microwave power in the reaction process, making temperature of reaction is 60 ℃～160 ℃.
3. the technology of preparation chitosan as claimed in claim 2, the weight percent concentration that it is characterized in that described alkali is 40～50%, temperature of reaction is 90 ℃～120 ℃.
4. the technology of preparation chitosan as claimed in claim 2, the slurry that it is characterized in that described discharge chitosan carries out suction filtration with the vacuum filtration machine, chitosan is separated with mother liquor, solid materials is a chitosan, mother liquor turns back to preparation alkaline solution operation deallocation material again, this mother liquor uses to a certain degree, reduce temperature, method with condensation-crystallization, sodium-acetate crystallization from the sodium acetate soln of degree of supersaturation is separated out, after the sodium-acetate that solution and crystallization are separated out separates with suction method, reclaim the by product sodium-acetate, at this moment mother liquor still returns the use of preparation alkaline solution operation, and sodium-acetate with the suction method washing several times, water lotion still returns use, becomes byproduct after the sodium-acetate drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99109831A CN1081644C (en) | 1999-07-16 | 1999-07-16 | Equipment and process for preparing chitin polyose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99109831A CN1081644C (en) | 1999-07-16 | 1999-07-16 | Equipment and process for preparing chitin polyose |
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| Publication Number | Publication Date |
|---|---|
| CN1280988A true CN1280988A (en) | 2001-01-24 |
| CN1081644C CN1081644C (en) | 2002-03-27 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99109831A Expired - Fee Related CN1081644C (en) | 1999-07-16 | 1999-07-16 | Equipment and process for preparing chitin polyose |
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| CN (1) | CN1081644C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747449B (en) * | 2008-11-28 | 2012-05-30 | 北京大学 | Nano chitosan derivative affinity matrix and preparation method and application thereof |
| CN101747448B (en) * | 2008-11-28 | 2012-07-04 | 北京大学 | Nano chitosan derivative and preparation method and application thereof |
| CN108946750A (en) * | 2018-06-13 | 2018-12-07 | 魏国庆 | It is a kind of to prepare bentonite method using acrylic acid production waste water |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4159932A (en) * | 1978-01-03 | 1979-07-03 | Peniston Quintin P | Process for activating chitin by microwave treatment and improved activated chitin product |
| RU2007796C1 (en) * | 1991-06-05 | 1994-02-15 | Институт радиотехники и электроники РАН | Chitin for absorption of electromagnetic energy in shf range |
-
1999
- 1999-07-16 CN CN99109831A patent/CN1081644C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747449B (en) * | 2008-11-28 | 2012-05-30 | 北京大学 | Nano chitosan derivative affinity matrix and preparation method and application thereof |
| CN101747448B (en) * | 2008-11-28 | 2012-07-04 | 北京大学 | Nano chitosan derivative and preparation method and application thereof |
| CN108946750A (en) * | 2018-06-13 | 2018-12-07 | 魏国庆 | It is a kind of to prepare bentonite method using acrylic acid production waste water |
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| Publication number | Publication date |
|---|---|
| CN1081644C (en) | 2002-03-27 |
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Granted publication date: 20020327 Termination date: 20110716 |