CN101948548B - Device and method for preparing dialdehyde starch from corn starch by photo-catalytic oxidation - Google Patents
Device and method for preparing dialdehyde starch from corn starch by photo-catalytic oxidation Download PDFInfo
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- 229920002085 Dialdehyde starch Polymers 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 20
- 229920002261 Corn starch Polymers 0.000 title claims abstract description 13
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 11
- 239000008120 corn starch Substances 0.000 title claims abstract 12
- 230000003647 oxidation Effects 0.000 title claims description 46
- 238000007254 oxidation reaction Methods 0.000 title claims description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 81
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 12
- 230000035484 reaction time Effects 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000005070 sampling Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 229940099112 cornstarch Drugs 0.000 claims abstract 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract 8
- 239000000706 filtrate Substances 0.000 claims abstract 2
- 230000001590 oxidative effect Effects 0.000 claims abstract 2
- 229920002472 Starch Polymers 0.000 claims description 42
- 235000019698 starch Nutrition 0.000 claims description 42
- 239000008107 starch Substances 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 26
- 238000003860 storage Methods 0.000 claims description 25
- 239000000498 cooling water Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims 3
- 239000007924 injection Substances 0.000 claims 3
- 230000001105 regulatory effect Effects 0.000 claims 3
- 239000012153 distilled water Substances 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 238000002834 transmittance Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000000967 suction filtration Methods 0.000 abstract description 4
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000013341 scale-up Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 12
- -1 weaving Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000002826 coolant Substances 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000013022 venting Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000019759 Maize starch Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 230000036760 body temperature Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
- 229940000406 drug candidate Drugs 0.000 description 1
- 239000003777 experimental drug Substances 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
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- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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Abstract
本发明涉及一种光催化氧化玉米淀粉制备双醛淀粉的装置和方法，属于化学工程、精细化工技术领域，本发明采用光促催化TiO2氧化玉米淀粉制取双醛淀粉，避免使用昂贵的高碘酸，且简易了实验装置，本发明通过紫外灯计时反应，反应时间为3h～20h，在取样口处取样分析，反应后的气、液、固三相混合物经过滤、除去TiO2催化剂，再向过滤液中加入丙酮，经抽滤、干燥后得到双醛淀粉，本发明工艺过程简单、连续性强、生产成本相对较低、易放大、实现工业化。
The invention relates to a device and method for preparing dialdehyde starch by photocatalytically oxidizing cornstarch, belonging to the technical fields of chemical engineering and fine chemical industry. The invention uses photocatalytic TiO2 to oxidize cornstarch to prepare dialdehydestarch, avoiding the use of expensive high iodic acid, and the experimental device is simple, the present invention reacts by ultraviolet lamp timing, the reaction time is 3h ~ 20h, samples are taken and analyzed at the sampling port, and the gas, liquid and solid three-phase mixture after the reaction is filtered to remove TiO2 Catalyst, and acetone is added to the filtrate, and the dialdehyde starch is obtained after suction filtration and drying. The process of the invention is simple, continuous, relatively low in production cost, easy to scale up, and industrialized.
Description
Technical field
The invention belongs to chemical engineering, field of fine chemical, the short catalyzed oxidation W-Gum of particularly a kind of light prepares the apparatus and method of dialdehyde starch.
Background technology
Dialdehyde starch is a kind of important chemical material, contains the aldehyde radical functional group of many easy reactions in its molecule, thereby has many excellent characteristic, like caustic solubility, is prone to cross-linked graft, and cohesive force is strong, easily gelatinization and be difficult for mouldy etc.Dialdehyde starch so have varied important purposes, is widely used in industries such as papermaking, process hides, building materials, glue, weaving, medicine, food because excellent materialization, biochemical property are arranged.The aldehyde radical of dialdehyde starch seldom exists with the free form.Its primary structure is and C6 primary hydroxyl group compound formation semi-acetal structure; The pure and mild semi-acetal of this potential semialdehyde is all very unstable; Being easy to fracture makes aldehyde radical dissociate out; Reactive behavior is identical with aldehyde compound, can react with acid or sulfite ion, alcohols, amine, amide substance, so dialdehyde starch has very high chemically reactive.
The outward appearance of dialdehyde starch is identical with ative starch, but physicochemical property and ative starch differ bigger, and dialdehyde starch is met the iodine blueness of failing in one's scheme, observation under polarizing microscope, particle black in color, no polarisation cross.Dialdehyde starch is insoluble to cold water, is dissolved in hot water, generates transparent film after the aqueous solution drying.
Along with the development of oxygenant recovery technology, the research of dialdehyde starch warms up once more.Dialdehyde starch has been realized large-scale industrial production abroad, still belongs to the starting stage in the production of China's dialdehyde starch and development.China is large agricultural country, and starch resource is very abundant, cheap, and therefore, the development research dialdehyde starch has great importance.Traditional dialdehyde starch preparation method makes oxygenant with Periodic acid 99 (salt), ydrogen peroxide 50 etc.; Preparation technology's original adoption single stage method; Be that starch oxidation becomes dialdehyde starch and acid iodide to be oxidized to Periodic acid 99 in same equipment, to carry out; Later stage is adopted two-step approach, and promptly starch oxidation becomes dialdehyde starch and acid iodide to be oxidized to Periodic acid 99 in same equipment, not carry out, and two kinds of methods respectively have relative merits.Because the price of Periodic acid 99 is very expensive, Periodic acid 99 must pass through recycling use during the preparation dialdehyde starch, to reduce cost; Again because Periodic acid 99 reclaims complex process, complex operation.As: blue flat; Liao Anping, people such as Lan Lihong be at " Guangxi University for Nationalities's journal " 2002, the last article of delivering of (3): 29-32 " preparation of dialdehyde starch and application "; Jurneng Zhen; Jianzhong Ma is at " Journal of the Society of leather Technologists andChemists " 2002,86 (3): the last article of delivering of 93-95 " Modification of starch andits application in leather making " and carry a red flag, Xu Wenjuan; Qin Xuejiang is in " paper and papermaking " 2002, the last article of delivering of (6): 42-44 " character of dialdehyde starch and improve the effect of paper wet tenacity ".The present invention is exactly prior art and the equipment deficiency for preparing dialdehyde starch to present W-Gum oxidation, designs, makes a kind of new and effective photo catalysis reactor and be applied to the W-Gum oxidation to prepare in the dialdehyde starch.
Summary of the invention
The present invention is exactly prior art and the equipment deficiency for preparing dialdehyde starch to present W-Gum oxidation; Design, make that a kind of novel operation is simple and easy, technological process is simple; Highly effective photocatalytic reactor that continuity is strong and method, and be applied to the W-Gum oxidation and prepare in the dialdehyde starch.
The present invention is achieved in that a kind of photochemical catalytic oxidation W-Gum of design prepares the device of dialdehyde starch; It is characterized in that; Comprise reaction tubes 23, storage vat 16, magnetic drive pump 20, said reaction tubes 23 is connected with bracket base through reaction tubes firm banking 3; Support 2 is connected in bracket base 1 and is connected with uv lamp 5 through ultraviolet lamp tube distance adjustment button 6; Reaction tubes 23 is provided with reaction tubes material outlet 24 and reaction tubes material inlet 26, and reaction tubes material outlet 24 places are provided with reaction tubes outlet material TM 22, and reaction tubes material inlet 26 places are provided with reaction tubes inlet temperature of charge meter 25; Said storage vat 16 is sent material into reaction tubes material inlet 26 through magnetic drive pump 20; In 16 barrels of the storage vats a barrel interior material thief hole 15 is installed; Sidepiece is equipped with cooling water jecket 17; The top is provided with storage vat venting hole 13, and wherein cooling water jecket 17 tops are provided with jacket water (J.W.) outlet 14, and the bottom is provided with cooling water inlet 19; Said magnetic drive pump is connected with Venturi spray tube 11, and is provided with under meter 7, the preceding variable valve 8 of meter and return valve 9, the preceding thief hole 10 of reaction and reaction back thief hole 21.Said Venturi spray tube 11 is provided with gas inlet 12, and said reaction tubes 23 is equipped with reaction tubes fixed strip 4; Said cooling water jecket 17 is equipped with feed temperature meter 18.Described reaction tubes size can be Ф 20 * 1.8 * 4800mm～Ф 14 * 1.8 * 200mm.
A kind of photochemical catalytic oxidation W-Gum prepares the method for dialdehyde starch, it is characterized in that, W-Gum is added zero(ppm) water; In thermostat water bath, slowly stir and be heated to 90 ℃, starch is all dissolved, solution is poured in the storage vat 16 of band cooling water jecket 17; In cooling water jecket, feed water coolant simultaneously, agitation as appropriate makes solution drop to 20 ℃～35 ℃ of room temperatures fast; Obtain unreacted plan homogeneous reaction liquid, take by weighing T
iO
2Catalyzer is also poured in the storage vat 16, opens magnetic drive pump 20, opens return valve 9, makes through Venturi spray tube 11 and sneaks into air in certain amount in the solution, obtains gas, liquid, solid three-phase mixture high dispersing, that certain transparence is arranged; Open the preceding variable valve 8 of meter and be transferred to certain flow, open uv lamp 5 clock reactions, the reaction times is 3h～20h, the sampling analysis at the thief hole place, and reacted gas, liquid, solid three-phase mixture is through filtering, remove T
iO
2Catalyzer adds acetone again in filtered liq, after suction filtration, drying, obtain dialdehyde starch.Described T
iO
2The mol ratio of catalyzer and W-Gum is 9.5～10.0, and the air capacity of said air is 13ml/min, and oxidisability is 38%.
The present invention has following characteristics: 1, technological process is simple.2, continuity is strong.3, production cost is relatively low.4, be prone to amplify, realize industriallization.
The present invention attempts adopting light to urge catalysis TiO
2Oxidised maize starch is produced dialdehyde starch, avoids the use of expensive Periodic acid 99, and simple and easy experimental installation.Semiconductor light-catalyst TiO
2After the rayed of wavelength less than 387nm, TiO
2The generation electron-hole pair that is excited, their people's life-span is a picosecond.Semi-conductor is because the existence in forbidden band makes that producing the electron hole can move to catalyst surface in its life-span.The H of isolating electronics of success and hole and photocatalyst surface absorption
2O or OH
-And O
2Reaction forms hydroxyl radical free radical and superoxide ion radical.The reactive group handle that these oxidation capacities are stronger is adsorbed on the starch oxidation of photocatalyst surface, and the C2 of starch AGU and C3 carbon atom hydroxyl are oxidized to aldehyde radical under the condition of gentleness, and the fracture of C2-C3 carbon bond gets dialdehyde starch.The radical hydroxyl that in reaction process, is generated is seldom, and its primary structure is to form the semi-acetal structure with the C6 primary hydroxyl group.The pure and mild hemiacetal linkage of these semialdehydes is all very unstable, is easy to fracture, makes aldehyde radical dissociate out; Reactive behavior is identical with aldehyde compound; Can react with materials such as acid or sulfite ion, alcohols, amine, acyl classes, therefore, dialdehyde starch has very high chemically reactive.In various industry, has wide application potential.Along with the arrival that oxygenant reclaims new technology, dialdehyde starch is in some countries commercialization.The dissolving of preparation dialdehyde starch under different condition, swelling, stability, rheological can produce great influence to the application of dialdehyde starch; And report seldom about the research of this respect; For this reason; We further investigate the synthetic and character of dialdehyde starch, for applying of dialdehyde starch provides theoretical direction.The factor that influences the dialdehyde content of dialdehyde starch responds the add-on of time, temperature of reaction, catalyzer and the time of activity and bubbling air etc.Our design experiment is to confirm optimal double starch aldehyde preparation technology for this reason.
Description of drawings
Below in conjunction with description of drawings and embodiment the present invention is further specified.
Fig. 1 prepares dialdehyde starch apparatus structure synoptic diagram for photochemical catalytic oxidation W-Gum of the present invention
Fig. 2 is the influence graph of a relation of temperature to starch oxidation
Fig. 3 is the influence graph of a relation of reaction times to starch oxidation
Fig. 4 is the influence graph of a relation of the add-on of catalyzer to starch oxidation
Fig. 5 is the influence graph of a relation of the air capacity of feeding to starch oxidation
1 bracket base among the figure; 2 supports; 3 reaction tubes firm bankings; 4 reaction tubes fixed strips; 5 uv lamps; 6 ultraviolet lamp tube distance adjustment buttons; 7 under meters; Variable valve before 8; 9 return valves; Thief hole before 10 reactions; 11 Venturi spray tubes; 12 gas inlets; 13 storage vat venting holes; The outlet of 14 jacket water (J.W.)s; Material thief hole in 15 barrels; 16 storage vats; 17 cooling water jeckets; 18 feed temperature meters; 19 cooling water inlets; 20 magnetic drive pumps; 21 reaction back thief holes; 22 reaction tubes outlet material TMs; 23 reaction tubess; 24 reaction tubes material outlets; 25 reaction tubess inlet temperature of charge meter; 26 reaction tubes material inlets.
Embodiment
As shown in Figure 1; Design the device that a kind of photochemical catalytic oxidation W-Gum prepares dialdehyde starch; Comprise reaction tubes 23, storage vat 16, magnetic drive pump 20, said reaction tubes 23 is connected with bracket base through reaction tubes firm banking 3; Support 2 is connected in bracket base 1 and is connected with uv lamp 5 through ultraviolet lamp tube distance adjustment button 6; Reaction tubes 23 is provided with reaction tubes material outlet 24 and reaction tubes material inlet 26, and reaction tubes material outlet 24 places are provided with reaction tubes outlet material TM 22, and reaction tubes material inlet 26 places are provided with reaction tubes inlet temperature of charge meter 25; Said storage vat 16 is sent material into reaction tubes material inlet 26 through magnetic drive pump 20; In 16 barrels of the storage vats a barrel interior material thief hole 15 is installed; Sidepiece is equipped with cooling water jecket 17; The top is provided with storage vat venting hole 13, and wherein cooling water jecket 17 tops are provided with jacket water (J.W.) outlet 14, and the bottom is provided with cooling water inlet 19; Said magnetic drive pump is connected with Venturi spray tube 11, and is provided with under meter 7, the preceding variable valve 8 of meter and return valve 9, the preceding thief hole 10 of reaction and reaction back thief hole 21.Said Venturi spray tube 11 is provided with gas inlet 12, and said reaction tubes 23 is equipped with reaction tubes fixed strip 4; Said cooling water jecket 17 is equipped with feed temperature meter 18.Described reaction tubes size can be Ф 20 * 1.8 * 4800mm～Ф 14 * 1.8 * 200mm.
Experimental drug and instrument: W-Gum: food grade, white powder, Changchun great achievement starch ltd; TiO
2Catalyzer: self-control; 37% hydrochloric acid, sodium hydroxide: analytical pure, Tianjin chemical reagent factory; Acetone: Ji Hua company 99.6%.PHS-3C acidometer Shanghai thunder magnetic instrument plant.
Experimental installation: see that the short catalyzed oxidation W-Gum of light prepares dialdehyde starch device accompanying drawing.
Experimental technique: accurate weighing W-Gum a certain amount of, that sieve through 300 order sub-sieves, in right amount in the there-necked flask of zero(ppm) water adding 10000mL, slowly stir in thermostat water bath and be heated to 90 ℃; Starch is all dissolved; Solution is poured in the storage vat of band cooling jacket, in cooling water jecket, fed water coolant, agitation as appropriate simultaneously; Make solution drop to room temperature (about 30 ℃) fast, obtain unreacted plan homogeneous reaction liquid.Take by weighing a certain amount of T
iO
2Catalyzer is also poured in the storage vat 16 that reaction solution is housed.Open magnetic drive pump 20, open return valve 9, make and sneak into air in certain amount (purity oxygen is better) in the solution, obtain gas, liquid, solid three-phase mixture high dispersing, that certain transparence is arranged.Open the preceding variable valve 8 of meter and be transferred to certain flow.Open the uv lamp clock reaction, timing is sampling analysis at the thief hole place, and reacted gas, liquid, solid three-phase mixture adds excessive propanone again through filtering, removing catalyzer in filtered liq, obtain dialdehyde starch through suction filtration, drying.
Analytical procedure: aldehyde group content (%)=(C
1V
1-2C
2V
2)/(G/160)/1000 * 100%
Wherein: C
1Concentration of sodium hydroxide solution, mol/L; V
1Sodium hydroxide solution volume mL; C
2Sulphuric acid soln concentration, mol/L; V
2The sulphuric acid soln volume, mL; G dialdehyde starch quality, g; 160 dialdehyde starch molecular masses.
Experimental result and discussion:
1). temperature is to the influence of starch oxidation degree
As shown in Figure 2, Fig. 2 is the influence graph of a relation of temperature to starch oxidation, its preparation condition: reaction times 3h, catalyzer add-on: starch: catalyzer (quality) is 10: 1, air feeding amount 12ml/min, reaction solution internal circulating load 500mL/min.
From graphic representation, can find out: the oxidation of starch degree increases gradually before 32 ℃; Flex point appears when 32 ℃ of left and right sides; The oxidation of starch degree increases little after 32 ℃.60-90 ℃ is constant basically, and flow state becomes unsmooth during near 90 ℃, this mainly since starch generation gelatinization cause.3h highest oxidation degree value is 38.9%.
2). the reaction times is to the influence of starch oxidation degree
Fig. 3 is the influence graph of a relation of reaction times to starch oxidation; As shown in Figure 3; Preparation condition: 20 ℃ of temperature of reaction, catalyzer add-on: starch: catalyzer (quality) is 10: 1, air feeding amount 12ml/min; It is being oxygenant with the potassium periodate that reaction solution internal circulating load 500mL/min.1,2,3 is respectively starch, adopts the different process the reaction time to the oxidisability influence curve.The 4th, starch under the photocatalyst effect circulating reaction near 10 hours oxidisability change curve.
From graphic representation, can find out: starch is under the photocatalyst effect, and its oxidisability increases in time gradually and increases, but speedup slows down after surpassing 10h.In experimentation, extend in time, the moisture in the reaction solution is taken out of gradually, therefore for relative concentration and the viscosity that guarantees reaction solution regularly keeps the skin wet, per hour increases water 5ml.
3). the add-on of catalyzer is to the influence of starch oxidation degree
Fig. 4 is the influence graph of a relation of the add-on of catalyzer to starch oxidation, and is as shown in Figure 4, preparation condition: 20 ℃ of temperature of reaction, reaction times 3h, air feeding amount 12ml/min, reaction solution internal circulating load 500mL/min.
From graphic representation, can find out: at catalyzer: material (starch) mol ratio is that the starch oxidation effect is best between 9.5～10.0 the time.This possibly be because airborne O
2, H
2O is at T
iO
2Under the effect, the hydroxy with strong oxidation of generation reaches finite concentration, and oxidation capacity has reached the summit.Catalytic amount very little, katalysis is not enough; Catalytic amount is excessive, and it is big that solution turbidity becomes, the light transmission variation, and oxidation capacity descends.
4) air capacity that feeds is to the influence of starch oxidation degree
Fig. 5 is the influence graph of a relation of the air capacity of feeding to starch oxidation, and is as shown in Figure 5, preparation condition: 20 ℃ of temperature of reaction, and reaction times 3h, catalyzer add-on: starch: catalyzer (quality) is 10: 1, reaction solution internal circulating load 500mL/mi n.
From graphic representation, can find out: before air capacity reached 13ml/min, the oxidation of starch degree increased gradually; Reach 13ml/min in air capacity and occur flex point later on, the oxidation of starch degree descends gradually.Reason possibly be to reach before the peak when oxidisability, and along with the increase of oxygen amount, the hydroxy with oxygenizement of generation is also increasing; Simultaneously, because oxygen is to be dispersed in the solution with the bubble state, owing to capillary reason; A large amount of catalyst distribution are arranged around bubble, have a certain amount of granules of catalyst a side a part not with the material joint, lose katalysis; And along with the increase of tolerance, the volume of bubble increases; The catalyzer that loses katalysis is many more, thereby causes oxidisability to reduce.If what feed is purity oxygen, the optimum gas value can reduce, and oxidisability also has increase slightly.The optimal air amount is 13ml/min, and oxidisability is about 38%.
5). the recovery of catalyzer and activation
Catalyst activation just is reentered into the catalyzer that filters to isolate and carries out roasting in the stove, utilizes again then.What be worth explanation is, because granules of catalyst is tiny, nearly has in the catalyst filtration sepn process that 17% catalyst stream loses, and promptly gets in the product mixed solution.T
iO
2Relative low price is mixed having necessarily with dialdehyde starch, request for utilization is tight promptly to the little occasion (as utilizing this dialdehyde starch and urea synthesis plank glue) of its product property influence.If will obtain purer dialdehyde starch, also need further refining.Life experiment does not carry out in the experiment.
Conclusion: experiment shows: utilize T
iO
2Catalyzer having under the uv lamp light action of certain intensity, can obtain dialdehyde starch.And under the constant situation of other conditions, oxidisability increases in time gradually and increases, and the oxidation of starch degree changes by steadily near after 32 ℃; Catalyzer: material (starch) mol ratio is that the starch oxidation effect is best between the 9.5-10.0 time; The optimum cycle reaction times is 10h.
Characteristics of the present invention: 1, technological process is simple.2, continuity is strong.3, production cost is relatively low.4, be prone to amplify, realize industriallization.
The content of still need further research, optimizing: the solvent of 1, select, preparation is more appropriate, make the solution light transmission better, improve photocatalysis efficiency.2, the active better catalyzer of preparation.3, prepare anti-solvent, the catalyzer of certain intensity is arranged, more convenient catalyzer separates with product.
The concrete operations mode is following:
1, W-Gum is added zero(ppm) water, in thermostat water bath, slowly stir and be heated to 90 ℃, starch is all dissolved; Solution is poured in the storage vat 16 of band cooling water jecket 17, concentration can not be too big, in cooling water jecket, feeds water coolant simultaneously; Agitation as appropriate; Make solution drop to 20 ℃～35 ℃ of room temperatures fast, obtain unreacted plan homogeneous reaction liquid, take by weighing T
iO
2Catalyzer is also poured in the storage vat 16, closes all valves.
2, start magnetic drive pump 20, open return valve 9, mixing solutions is circulated, purpose has two: one, guarantees that mixing solutions does not form deposition in the storage vat; The 2nd, under the effect of Venturi spray tube 11, make and disperse some air in the mixing solutions, form gas-liquid mixture highly uniformly, for next step reaction provides competent oxygen, also simplified technology simultaneously.
3, open the preceding variable valve 8 of meter, be adjusted to certain flow, also keep stable.
4, open uv lamp 5, the reaction times is 3h～20h, feeds water coolant to the storage vat chuck simultaneously.Cooling purpose: on the one hand keep reacting liquid temperature, prevent that liquid in the reaction tubes, body temperature are too high; Too high when reacting liquid temperature on the other hand, soltion viscosity increases, mobile variation.Simultaneously, the light transmission variation influences catalytic effect.
5, data such as recording reacting time, storage vat internal reaction liquid temp, flow in the reaction, and on time before react thief hole 10, thief hole 21 samplings of reaction back detect, analyze.
6, when thief hole 10 before react, thief hole 21 samplings of reaction back detect, analytical data near the time, stop experiment.
When 7, experiment finishes, close uv lamp earlier, stop product pump again, close water coolant at last.
8, reacted gas, liquid, solid three-phase mixture is through filtering, remove T
iO
2Catalyzer adds acetone again in filtered liq, after suction filtration, drying, obtain dialdehyde starch, described T
iO
2The mol ratio of catalyzer and W-Gum is 9.5～10.0, and the air capacity of said air is 13ml/min, and oxidisability is 38%.
Should be specifically noted that in the operation:
1, in strict accordance with implementation method operation, assurance device steady running.
2, suitably regulate mass flow, guarantee that material is smooth and easy and flow, deposition does not appear.
3, suitably regulate not overtemperature degree of cooling water flow, assurance material, certain flowability is arranged.
Claims (7)
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102304291A CN101948548B (en) | 2010-07-20 | 2010-07-20 | Device and method for preparing dialdehyde starch from corn starch by photo-catalytic oxidation |
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| CN2010102304291A CN101948548B (en) | 2010-07-20 | 2010-07-20 | Device and method for preparing dialdehyde starch from corn starch by photo-catalytic oxidation |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0041316A1 (en) * | 1980-04-25 | 1981-12-09 | Cpc International Inc. | Method of modifying starch |
| EP0046347A1 (en) * | 1980-08-07 | 1982-02-24 | Cpc International Inc. | Method of modifying starch |
| CN1273390A (en) * | 1999-05-06 | 2000-11-15 | 国际商业机器公司 | Method and equipment for effective calling Java method from local code |
| CN1420087A (en) * | 2002-12-24 | 2003-05-28 | 同济大学 | Fixed membrane optocatalytic oxidation water treating system |
| CN1508073A (en) * | 2002-12-19 | 2004-06-30 | 石油大学(北京) | Fluidized photocatalytic reactor and process for purifying waste water using the reactor |
-
2010
- 2010-07-20 CN CN2010102304291A patent/CN101948548B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0041316A1 (en) * | 1980-04-25 | 1981-12-09 | Cpc International Inc. | Method of modifying starch |
| EP0046347A1 (en) * | 1980-08-07 | 1982-02-24 | Cpc International Inc. | Method of modifying starch |
| CN1273390A (en) * | 1999-05-06 | 2000-11-15 | 国际商业机器公司 | Method and equipment for effective calling Java method from local code |
| CN1508073A (en) * | 2002-12-19 | 2004-06-30 | 石油大学(北京) | Fluidized photocatalytic reactor and process for purifying waste water using the reactor |
| CN1420087A (en) * | 2002-12-24 | 2003-05-28 | 同济大学 | Fixed membrane optocatalytic oxidation water treating system |
Non-Patent Citations (1)
| Title |
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| 桂伟等.动态循环污水光催化处理装置的设计.《机械制造》.2010,第48卷(第550期),第4-6页. * |
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