CN102584838A - Natural ferrous aluminum chlorophyll and preparation method thereof - Google Patents
Natural ferrous aluminum chlorophyll and preparation method thereof Download PDFInfo
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- CN102584838A CN102584838A CN2012100140794A CN201210014079A CN102584838A CN 102584838 A CN102584838 A CN 102584838A CN 2012100140794 A CN2012100140794 A CN 2012100140794A CN 201210014079 A CN201210014079 A CN 201210014079A CN 102584838 A CN102584838 A CN 102584838A
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- iron
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- chlorophyllin
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Abstract
The invention discloses a preparation method of natural ferrous aluminum chlorophyll, which is used for preparing natural ferrous aluminum chlorophyll (also named aluminum ferrous chlorophyll). In the method, sodium ferrous chlorophyllin and an aluminum salt are taken as raw materials and are substituted directly to obtain the natural ferrous aluminum chlorophyll in one step. The method comprises the following steps of: dissolving the sodium ferrous chlorophyllin and the aluminum salt into water and a buffer solution according to a certain mass ratio, wherein the pH value of a reaction solution is 7.5-9; slowly adding an aluminum salt solution into a sodium ferrous chlorophyllin solution, stirring magnetically at the speed of 1,000 revolutions per minute, and reacting fully; and aging, separating, and drying at the temperature of 50-80 DEG C to obtain black (deep green) ferrous aluminum chlorophyll. The preparation method has the advantages of easiness, convenience, low cost, no production of side products, environmental friendliness and high yield. Raw materials needed by synthesis are readily-available, have low prices, are nontoxic and harmless, and have indefinite development and application prospects on the aspect of medical medicaments, functional materials and the like.
Description
Technical field
The present invention relates to a kind of natural pigment salt and preparation method thereof, specifically a kind of preparation method of natural phyllo-iron aluminium salt.The natural phyllo-iron aluminium salt that obtains is also claimed iron chlorophyllin aluminium.
Background technology
Chlorophyll is a kind of important magnesium porphyrin compound, belongs to natural pigment, and its verivate kind is also a lot.As: Copper chlorophyllin a sodium salt, calcium CHLOROPHYLLINE sodium salt, cobalt CHLOROPHYLLINE sodium salt, iron chlorophyllin sodium salt etc. all have application in industries such as chemical industry, medicine, food, health cares.Like foodstuff additive as candy, cake, animal-feed etc.; As make perfumed soap, perfume, etc. the additive of product; Also can treat cancer, tumour, hematopoiesis, protect the liver etc.Patent of the present invention institute synthetic natural phyllo-iron aluminium salt also has purposes aspect medical; Because; The medicine for enterogastritis of the treatment hyperchlorhydria of selling on the market at present, stomach ulcer etc. all contains aluminium component more than 80%; Comprise aluminum hydroxide gel, Tai-Ace S 150, hydrotalcite, sucralfate etc., taking one of these type of Side effects of pharmaceutical drugs for a long time is anaemia.And the structure of the protoheme in chlorophyll structure and the human blood is extremely similar in the chlorophyll iron aluminium salt, if therefore can alleviate other with institute's synthetic chlorophyll iron aluminium salt to a certain extent as stomach medicine composition contains the spinoff that aluminium stomach medicine brings, anaemia.In addition, because pyrrole quinoline ring particular structural makes this compound have many premium propertiess, like photosensitivity etc., so development and application values is also still arranged on functional materials.
Existing phyllins mainly are to replace the center magnesium elements with other metals ions, or replace the hydrogen salify on the outer carboxyl of porphyrin ring with sodium ion.The salifiable situation of hydrogen is at present rarely seen to have two pieces of reports (referring to the 1. preparation method of the refined duckweed ZL200710061547.2. of Liu natural phyllo-iron zinc salt and replace with other metals ions; 2. the extra large roc of making pottery. the preparation of pheophorbide calcium. West China pharmacy will .2002,17 (2): 120).Through retrieval, natural phyllo-iron aluminium salt and do not see also that with the sodium-iron-chlorophyllin technical scheme that turns to chlorophyll iron aluminium salt of deriving report is arranged.
Summary of the invention
A kind of new phyllins have been the objective of the invention is to synthesize, chlorophyll iron aluminium salt; And to provide a kind of be raw material with the sodium-iron-chlorophyllin, and with the carboxyl sodium on the direct substitution sodium-iron-chlorophyllin of trivalent aluminium ion, a step is processed the method for the high natural phyllo-iron aluminium salt of purity with single factor rotation method; This method is simple to operation; Product is pure, environmentally safe, and productive rate is high.
In order to realize the foregoing invention purpose, the present invention has adopted following technical scheme:
A kind of preparation method of natural phyllo-iron aluminium salt, it is raw material with sodium-iron-chlorophyllin and aluminum trichloride (anhydrous), and is direct substitution, a step processes.
Particularly, chlorophyll iron aluminium salt preparation method of the present invention may further comprise the steps:
1, sodium-iron-chlorophyllin and aluminum trichloride (anhydrous) mass ratio are 2: 1.Sodium-iron-chlorophyllin is soluble in water, and aluminum trichloride (anhydrous) is with the buffered soln dissolving of pH=7;
2, be that 6.0～7.0 aluminum salt solution slowly adds in the sodium iron chlorophyllin salts solution with the pH value;
3, reacting liquid pH value is 7～8.5;
4, stir with turn left right speed of 1000r/min, make its sufficient reacting under the room temperature;
5, ageing 5～8h under the room temperature (17～25 ℃);
6, filtering separation, 50 ℃～80 ℃ dryings can obtain black (blue black is green) chlorophyll iron aluminium salt.Above-mentioned numerical range can arbitrary combination, does not have inevitable corresponding relation.
Through spectrophotometric analysis product iron content, aluminium amount, the calculating productive rate is: 83%～90%.Through colour-change and sedimentary generation and UV spectrogram, IR spectrogram and DTA in the preparation, explain that product is a chlorophyll iron aluminium salt.
Remarkable advantage of the present invention is that 1. synthetic desired raw material all is easy to get, and is cheap, and nontoxic, and product chlorophyll iron aluminium salt is black or claims blue black green crystal small-particle, has metalluster.In water insoluble and the Hydrogen chloride, be slightly soluble in acetone, solution is yellow-green colour, is dissolved in 1: 1 slightly and is green in the hydrochloric acid, and being soluble in pH is must yellow-green soln in the 12 above basic solns.2. the preparation method is simple and direct, cost is low, does not produce by product, environmentally safe, and productive rate is high.3. application potential is big, all has unlimited development prospect at aspects such as Medicines, functional materialss.
Description of drawings
Fig. 1 is the UV abosrption spectrogram of sodium iron chlorophyllin acetone soln.
Fig. 2 is the UV abosrption spectrogram of chlorophyll iron aluminium acetone soln.
Fig. 3 is the IR spectrogram of sodium iron chlorophyllin.
Fig. 4 is the IR spectrogram of chlorophyll iron aluminium.
Fig. 5 is the differential thermal analysis curve of sodium iron chlorophyllin.
Fig. 6 is the differential thermal analysis curve of chlorophyll iron aluminium.
Embodiment
Below in conjunction with concrete accompanying drawing and with embodiment the present invention is done further description.
The key instrument that the present invention uses: pH meter (the Sai Duolisi pB-10 of Germany); 766-3 far-infrared radiation loft drier (Shanghai sunlight laboratory apparatus ltd); Digital display constant temperature blender with magnetic force HJ-3 (Hangzhou remittance that instrument); The AEL-160 electronic balance; UV7652 spectrophotometer (Shanghai Precision Scientific Apparatus Co., Ltd); AVATAR360 Fourier transformation infrared spectrometer (U.S. Nicolet company); ZCR-1 differential thermal analyzer (Nanjing Sang Li).
The main medicine that the present invention uses:
Sodium-iron-chlorophyllin (the extensively logical precious medical ltd in Shandong); Aluminum trichloride (anhydrous) (AR, Tianjin Da Mao chemical reagent factory).
Water-soluble its strength of solution of sodium-iron-chlorophyllin 0.67g/100ml, the pH value is 8.5.It is 7 buffered soln that aluminum trichloride (anhydrous) is dissolved in pH, and its pH value of solution is 6.8.Aluminum salt solution is slowly added in the sodium-iron-chlorophyllin.Stir with turn left right speed of 1000r/min, make its sufficient reacting under the room temperature.Ageing 5h under the room temperature.Separate, 80 ℃ of dryings can obtain chlorophyll iron aluminium salt.Productive rate is 85%.Carry out each index determining.Wherein,, obtain sodium-iron-chlorophyllin and chlorophyll iron aluminium salt spectrogram (seeing accompanying drawing 1～6), and analyse and compare, confirm that product is a chlorophyll iron aluminium salt through AVATAR360 type Fourier transformation infrared spectrometer, UV7652 spectrophotometer and ZCR-1 differential thermal analyzer.
Embodiment 2
Water-soluble its pH value of solution of sodium-iron-chlorophyllin is 8.9.It is 7 buffered soln that aluminum trichloride (anhydrous) is dissolved in pH, and its pH value of solution is 6.6.Aluminum salt solution is slowly added in the sodium-iron-chlorophyllin.Stir with turn left right speed of 1000r/min, make its sufficient reacting under the room temperature.Room temperature ageing 7h.Separate, 60 ℃ of dryings can obtain chlorophyll iron aluminium salt.Calculating productive rate is 89%.
Embodiment 3
Water-soluble its pH value of solution of sodium-iron-chlorophyllin is 8.1.It is 7 buffered soln that aluminum trichloride (anhydrous) is dissolved in pH, and its pH value of solution is 6.2.Aluminum salt solution is slowly added in the sodium-iron-chlorophyllin.Stir with 1000r/min left and right sides speed, room temperature (17～25 ℃) is digestion time 9h down.Separate, 50 ℃ of dryings can obtain chlorophyll iron aluminium salt.Calculating productive rate is 87%.
Chlorophyll iron aluminium salify is analyzed:
1, change from experimental phenomena, with sodium iron chlorophyllin water-soluble after, solution colour is blackish green, adds Al
3+During the reagent salify, produce black precipitate immediately, explained that novel substance generates.
2, ultraviolet-visible (UV) absorption spectrum map analysis
Referring to accompanying drawing 1,2 and following table.From the UV spectrum analysis; At first sodium-iron-chlorophyllin is similar with the peak position of chlorophyll iron aluminium salt in the peak position of 364.5nm, 400.5nm and 666.5nm; But at the 502.0nm place, the red shift of chlorophyll iron aluminium salt is to 529.0nm, this sodium in the sodium-iron-chlorophyllin that possibly be aluminium substitution.Former because aluminum ion electronegativity 1.61; The electronegativity 0.93 of sodium ion, the electronegativity difference in the feasible compound that forms of aluminum ion replacement sodium ion between metal and the carboxyl reduces, and moment of dipole also reduces; Then the division of the molecular orbital(MO) of chlorophyll iron aluminium salt reduces, and red shift takes place.
Table iron chlorophyllin aluminium and sodium iron chlorophyllin ultraviolet-visible figure spectrum peak position, absorbancy
3, ir spectra map analysis (IR)
Referring to collection of illustrative plates 3,4, by the IR spectrum analysis, sodium-iron-chlorophyllin and chlorophyll iron aluminium salt are at 2000cm
-1Before, basic indifference, but at 1600cm
-1About occur differently, ferrisodium salt is respectively at 1634.6cm
-1And 1563.58cm
-1Two characteristic frequencies are arranged, and iron aluminium salt is only at 1634.6cm
-1The place has one.1900～1600cm
-1The stretching vibration frequency that in the zone is carboxyl is along with substituent difference, and absorption frequency changes, and in addition, two figure also have bigger difference in the fingerprint region, and the absorption frequency of ferrisodium salt is at 673.14cm
-1, 471.02cm
-1Than iron aluminium salt at 684.08cm
-1, 558,42cm
-1Difference blue shift 11cm
-1And 87cm
-1, this is similar with UV spectrum gained conclusion.The spectrum more complicated that this is regional, be because between the various single bonded stretching vibrations and and the C-H formation vibration between the result of coupling takes place mutually, and very responsive to variation small on the structure, confirmed that further aluminum ion replaces the sodium ion salify.
4, DTA
Referring to collection of illustrative plates 5,6, by the differential thermal atlas analysis, sodium-iron-chlorophyllin is that crystalline network is destroyed in the heat-processed at first peak of 200～210 ℃, becomes lattice reconstruct, the exothermic peak of formation take place behind the amorphous substance.Second peak is Fe
2+Be oxidized to Fe
3+The peak that heat release forms, temperature is at 340～450 ℃.
Because the chlorophyll iron aluminium salt quality that generates is hard than ferrisodium salt, the lattice damage temperature raises, and becomes 220～230 ℃, and Fe
2+Be oxidized to Fe
3+The peak that heat release forms also exists, and possibly cause two peaks to be overlapped because aluminum ion replaces the sodium ion recurring structure to be changed.
In sum, can confirm that product is a chlorophyll iron aluminium salt.
Although the preceding text specific embodiments of the invention has given to describe in detail and explanation; But should indicatedly be; We can carry out various equivalences to above-mentioned embodiment according to conception of the present invention and change and modification; When the function that it produced does not exceed spiritual that specification sheets contains yet, all should be within protection scope of the present invention.
Claims (3)
1. natural phyllo-iron aluminium salt and preparation method thereof is characterized in that, with the sodium ion on the direct substitution carboxyl of trivalent aluminium ion, a step processes through single factor rotation method, obtains natural phyllo-iron aluminium salt, also claims iron chlorophyllin aluminium.
2. the method for claim 1, it is characterized in that: with sodium-iron-chlorophyllin and aluminum trichloride (anhydrous) is raw material, prepares.
3. according to claim 1 or claim 2 method may further comprise the steps:
1) sodium-iron-chlorophyllin and aluminum trichloride (anhydrous) mass ratio are 2: 1, and the former is soluble in water, and it is 7 buffered soln that the latter is dissolved in the pH value;
2) be that 6.0～7.0 aluminum salt solution slowly adds in the sodium-iron-chlorophyllin with the pH value;
3) reaction solution pH is 7.5～9;
4) stir with turn left right speed of 1000r/min, make its sufficient reacting under the room temperature;
5) room temperature sinkingization, digestion time 4～9h;
6) separate, 50 ℃～80 ℃ dryings can obtain black or claim dark blackish green chlorophyll iron aluminium salt; Through spectrophotometric analysis product iron content, aluminium amount, the calculating productive rate is: 83%～90%; Become very shallow yellow and the sedimentary generation of black thing through solution colour in the preparation process by blackish green, and UV spectrogram and IR spectrum analysis, explain that product is a chlorophyll iron aluminium salt.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757439A (en) * | 2012-07-30 | 2012-10-31 | 河北联合大学 | Natural cobalt iron chlorophyllin and preparation method thereof |
| CN102757438A (en) * | 2012-07-30 | 2012-10-31 | 河北联合大学 | Natural nickel ferrous chlorophyll salt and preparation method thereof |
| CN102796108A (en) * | 2012-07-30 | 2012-11-28 | 河北联合大学 | Natural chlorophyll iron-manganese salt and preparation method thereof |
| CN109463491A (en) * | 2019-01-07 | 2019-03-15 | 刘安军 | A kind of instant green tea and preparation method thereof rich in chlorophillins |
Citations (4)
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|---|---|---|---|---|
| WO2002016366A1 (en) * | 2000-08-23 | 2002-02-28 | Itoi Textile Co., Ltd | Copper or iron chlorophyllin sodium, pulp, aqueous pigment solution, paper yarn and process for producing the same |
| JP2006151874A (en) * | 2004-11-30 | 2006-06-15 | Meisei Kagaku Kogyo Kk | Dimer of chlorophyll derivative, its metal complex and method for oxidizing organic compound by using the same as catalyst |
| CN101045730A (en) * | 2007-02-15 | 2007-10-03 | 河北理工大学 | Preparation method of natural phyllo-iron zinc salt |
| CN102311441A (en) * | 2011-10-21 | 2012-01-11 | 四川通世达生物科技有限公司 | Production method of sodium copper chlorophyllin |
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2012
- 2012-01-18 CN CN2012100140794A patent/CN102584838A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002016366A1 (en) * | 2000-08-23 | 2002-02-28 | Itoi Textile Co., Ltd | Copper or iron chlorophyllin sodium, pulp, aqueous pigment solution, paper yarn and process for producing the same |
| JP2006151874A (en) * | 2004-11-30 | 2006-06-15 | Meisei Kagaku Kogyo Kk | Dimer of chlorophyll derivative, its metal complex and method for oxidizing organic compound by using the same as catalyst |
| CN101045730A (en) * | 2007-02-15 | 2007-10-03 | 河北理工大学 | Preparation method of natural phyllo-iron zinc salt |
| CN102311441A (en) * | 2011-10-21 | 2012-01-11 | 四川通世达生物科技有限公司 | Production method of sodium copper chlorophyllin |
Non-Patent Citations (1)
| Title |
|---|
| 孙彩云,等: "蚕沙制备叶绿素锌钾盐的工艺研究", 《化学与生物工程》, no. 5, 30 May 2005 (2005-05-30), pages 33 - 34 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757439A (en) * | 2012-07-30 | 2012-10-31 | 河北联合大学 | Natural cobalt iron chlorophyllin and preparation method thereof |
| CN102757438A (en) * | 2012-07-30 | 2012-10-31 | 河北联合大学 | Natural nickel ferrous chlorophyll salt and preparation method thereof |
| CN102796108A (en) * | 2012-07-30 | 2012-11-28 | 河北联合大学 | Natural chlorophyll iron-manganese salt and preparation method thereof |
| CN109463491A (en) * | 2019-01-07 | 2019-03-15 | 刘安军 | A kind of instant green tea and preparation method thereof rich in chlorophillins |
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Application publication date: 20120718 |