A method for preparing a complex pectic polysaccharide

Abstract

The application discloses a preparation method of a complex pectin polysaccharide applied to the field of pectin polysaccharide preparation, which uses citrus and legume peel residues as raw materials, adopts a medium-high temperature dilute acid hydrolysis technology to prepare a polysaccharide concentrated solution, uses divalent cations mainly including calcium ions as a crosslinking agent, makes part of linear structure pectin polysaccharides and globular structure pectin polysaccharides form calcium bridges through ionic bonds to produce crosslinking, uses organic carboxylate as a chelating agent, controls the calcium bridge crosslinking in a proper range through part of divalent cations in the chelating system, avoids excessive calcium crosslinking and produces insoluble pectin polysaccharides, uses alcohol as a dehydrating agent to remove the hydration film on the surface of part of pectin polysaccharides, simultaneously inhibits the dissociation of carboxyl groups on part of pectin polysaccharide molecules through hydrogen ions, promotes part of linear pectin polysaccharides and globular pectin polysaccharides to produce crosslinking under the action of hydrogen bonds, and finally forms the complex pectin polysaccharide which is mainly crosslinked by calcium bridges and supplemented by hydrogen bonds.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of pectin polysaccharide preparation, in particular to a preparation method of complex pectin polysaccharide. BACKGROUND

[0002] Pectin polysaccharide is widely distributed in the primary cell wall and intercellular space of roots, stems, leaves, fruits and other tissues of higher plants, and plays a softening and adhesive role in cell tissues, and is a support material for internal cells, directly affecting the integrity and firmness of plant tissues, and is also a natural barrier to resist the invasion of pathogenic microorganisms.

[0003] At present, the raw materials of commercial pectin are mainly lemon peel, orange peel and apple pomace, in addition, sugar beet waste, sunflower disc and mango pomace also contain rich pectin, which can be used as raw materials for pectin production. Pectin from different sources has differences in molecular weight, degree of methylation, and number of other groups, resulting in different physicochemical and functional properties, and the stability of existing pectin polysaccharide is also poor.

[0004] Therefore, we solve the problem of unstable pectin system in the existing preparation method through the technical scheme. SUMMARY

[0005] The present application aims to improve the preparation method in the prior art, and provides a preparation method of complex pectin polysaccharide compared with the prior art, which uses citrus peel and legume peel as raw materials, adopts medium-high temperature dilute acid hydrolysis technology, prepares polysaccharide concentrate, uses divalent cations such as calcium ions as cross-linking agent, makes part of linear structure pectin polysaccharide and globular structure pectin polysaccharide form calcium bridge and cross-link through ionic bond, uses organic carboxylate as chelating agent, chelates part of divalent cations in the system, controls the calcium bridge cross-linking in a proper range to avoid excessive calcium cross-linking and produce insoluble pectin polysaccharide, uses alcohol as dehydrating agent to remove part of the hydration film on the surface of pectin polysaccharide, and at the same time, inhibits the dissociation of carboxyl groups on part of pectin polysaccharide molecules through hydrogen ions, promotes the cross-linking of part of linear pectin polysaccharide and globular pectin polysaccharide under the action of hydrogen bond, and finally forms complex pectin polysaccharide with calcium bridge cross-linking as the main role and hydrogen bond cross-linking as the auxiliary role.

[0006] Optionally, the automatic liquid adding device in S3 comprises a liquid storage cylinder and a liquid adding bucket, the liquid storage cylinder is filled with organic carboxylate solution, the middle part of the liquid adding bucket is fixedly embedded with a liquid adding pipe in communication with the liquid storage cylinder, the upper end of the liquid adding bucket is provided with a control cavity in communication with the liquid adding pipe, one side of the lower end of the liquid adding bucket is provided with a PH value monitoring rod, and the inside of the liquid adding bucket is provided with an analyzer electrically connected with the PH value monitoring rod, the analyzer comprises a PH value monitoring module, a PH value setting module and a liquid adding start-stop module, both sides of the control cavity are provided with a micro electromagnetic iron, the liquid adding start-stop module is electrically connected with the micro electromagnetic iron through a control processor, both sides of the control cavity are slidably and sealingly connected with a moving magnetic plate repelling the micro electromagnetic iron, and the moving magnetic plates are fixedly connected with a variable liquid passing plate between them, the lower end of the variable liquid passing plate is fixedly connected with a liquid sealing ball in the middle part, and a plurality of through holes are formed in the variable liquid passing plate, the upper end of the liquid adding pipe is fixedly connected with a liquid sealing door matched with the liquid sealing ball, and the liquid sealing door is below the liquid sealing ball, the organic carboxylate solution is added by the automatic liquid adding device, the inaccuracy of manual liquid adding is effectively avoided, the automatic liquid adding device is hung in the concentrated solution and the PH value monitoring rod is immersed in the concentrated solution to monitor the PH value in real time, the PH value to be adjusted is set by the PH value setting module, the micro electromagnetic iron is started by the liquid adding start-stop module, the moving magnetic plate is repelled by the micro electromagnetic iron, and the variable liquid passing plate is curved and arched, the variable liquid passing plate is separated from the liquid sealing door after being arched, the organic carboxylate solution in the liquid storage cylinder flows into the concentrated solution below to adjust the PH value, the PH value monitoring rod monitors the PH value of the concentrated solution in real time, and the micro electromagnetic iron is paused by the liquid adding start-stop module when the monitored PH value reaches the set value, at this time, the variable liquid passing plate restores to the original shape under the action of its own elastic force, the liquid sealing ball recontacts with the liquid sealing door, and the automatic liquid adding is stopped.

[0007] Further, a plurality of elastic embedded rods are fixedly embedded in the inner wall of the variable liquid passing plate, and the variable liquid passing plate is made of polyurethane elastic material, the elastic embedded rods enable the variable liquid passing plate to have restoring elasticity, so that the variable liquid passing plate restores to the original shape under the elastic force of the elastic embedded rods after the micro electromagnetic iron is turned off, the liquid sealing ball recontacts with the liquid sealing door, and the downward flow channel of the organic carboxylate solution is closed.

[0008] Further, a plurality of elastic embedded rods are fixedly embedded in the inner wall of the variable liquid passing plate, and the variable liquid passing plate is made of polyurethane elastic material, the elastic embedded rods enable the variable liquid passing plate to have restoring elasticity, so that the variable liquid passing plate restores to the original shape under the elastic force of the elastic embedded rods after the micro electromagnetic iron is turned off, the liquid sealing ball recontacts with the liquid sealing door, and the downward flow channel of the organic carboxylate solution is closed.

[0009] Further, a plurality of elastic embedded rods are fixedly embedded in the inner wall of the variable liquid passing plate, and the variable liquid passing plate is made of polyurethane elastic material, the elastic embedded rods enable the variable liquid passing plate to have restoring elasticity, so that the variable liquid passing plate restores to the original shape under the elastic force of the elastic embedded rods after the micro electromagnetic iron is turned off, the liquid sealing ball recontacts with the liquid sealing door, and the downward flow channel of the organic carboxylate solution is closed.

[0010] Further, the liquid storage cylinder is made of corrosion-resistant transparent material, and the outer surface of the liquid storage cylinder is provided with scale lines, so as to facilitate the checking of the remaining amount of the organic carboxylate solution.

[0011] Compared with the prior art, the application has the following advantages:

[0012] (1) The scheme uses citrus peel residues and legume peel residues as raw materials, adopts a medium-high temperature dilute acid hydrolysis technology, and prepares a polysaccharide concentrate. Calcium ions are used as divalent cations as a crosslinking agent. The carboxyl groups of part of linear structure pectin polysaccharides and globular structure pectin polysaccharides form calcium bridges by ionic bonds to produce crosslinking. An organic carboxylate is used as a chelating agent. Part of the divalent cations in the chelating system control the calcium bridge crosslinking in a proper range to avoid excessive calcium crosslinking and the formation of insoluble pectin polysaccharides. Alcohol is used as a dehydrating agent to remove part of the hydration film on the surface of the pectin polysaccharides. At the same time, hydrogen ions inhibit the dissociation of the carboxyl groups on part of the pectin polysaccharide molecules, promote the crosslinking of part of the linear pectin polysaccharides and globular pectin polysaccharides under the action of hydrogen bonds, and finally form a complex pectin polysaccharide in which linear and globular molecules are crosslinked mainly by calcium bridge action and supplemented by hydrogen bond action.

[0013] (2) The automatic liquid feeder in the S3 step comprises a liquid storage cylinder and a liquid adding hopper, the liquid storage cylinder is filled with organic carboxylate solution, the middle part of the liquid adding hopper is fixedly embedded with a liquid adding pipe in communication with the liquid storage cylinder, the inner wall of the upper end of the liquid adding hopper is provided with a control cavity in communication with the liquid adding pipe, one side of the lower end of the liquid adding hopper is provided with a PH value monitoring rod, and the inside of the liquid adding hopper is provided with an analyzer electrically connected with the PH value monitoring rod, the analyzer comprises a PH value monitoring module, a PH value setting module and a liquid adding start-stop module, both sides of the control cavity are provided with a micro electromagnetic iron, the liquid adding start-stop module is electrically connected with the micro electromagnetic iron through a control processor, both sides of the control cavity are slidably and sealingly connected with a moving magnetic plate repelling the micro electromagnetic iron, and the two moving magnetic plates are fixedly connected with a variable liquid passing plate between them, the lower end of the variable liquid passing plate is fixedly connected with a liquid sealing ball in the middle part, and a plurality of through holes are formed in the variable liquid passing plate, the inner wall of the upper end of the liquid adding pipe is fixedly connected with a liquid sealing door matched with the liquid sealing ball, and the liquid sealing door is below the liquid sealing ball, the organic carboxylate solution is added through the automatic liquid feeder, the inaccuracy of manual liquid adding is effectively avoided, the automatic liquid feeder is hung in the concentrated liquid and the PH value monitoring rod is immersed in the concentrated liquid to monitor the PH value in real time, the PH value to be adjusted is set through the PH value setting module, the micro electromagnetic iron is started through the liquid adding start-stop module, the moving magnetic plate is repelled by the micro electromagnetic iron, and the variable liquid passing plate is bent and arched, the variable liquid passing plate is separated from the liquid sealing door after being arched, so that the organic carboxylate solution filled in the liquid storage cylinder flows into the concentrated liquid below to adjust the PH value, the PH value monitoring rod monitors the PH value of the concentrated liquid in real time, and the micro electromagnetic iron is paused immediately through the liquid adding start-stop module when the monitored PH value reaches the set value, at this time, the variable liquid passing plate restores to the original shape under the action of its own elastic force, the liquid sealing ball is in close contact with the liquid sealing door again, and thus the automatic liquid adding is stopped.

[0014] (3) A plurality of elastic embedded rods are fixedly embedded in the inner wall of the variable liquid passing plate, and the variable liquid passing plate is made of polyurethane elastic material, the elastic embedded rods enable the variable liquid passing plate to have restoring elasticity, so that the variable liquid passing plate restores to the original shape under the elastic force of the elastic embedded rods after the micro electromagnetic iron is turned off, so that the liquid sealing ball is in contact with the liquid sealing door again, and thus the downward flow channel of the organic carboxylate solution is closed.

[0015] (4) A liquid leakage hole matched with the liquid sealing ball is formed in the liquid sealing door, and a magnetic pad magnetically attracted to the liquid sealing ball is fixedly connected to the liquid leakage hole, the liquid sealing ball is in close contact with the liquid leakage hole on the liquid sealing door, thereby playing a sealing role, and the magnetic pad further effectively improves the sealing effect and effectively prevents the organic carboxylate solution from leaking.

[0016] (5) The magnetic pad is further covered with a security pad made of silica gel, and a layer of security pad is added to the outer layer of the magnetic pad to improve the sealing effect of the liquid sealing ball and the liquid leakage hole and effectively prevent the solution from leaking.

[0017] (6) The liquid storage cylinder is made of corrosion-resistant transparent material, and the outer surface of the liquid storage cylinder is provided with scale lines. In order to facilitate the checking of the remaining amount of the organic carboxylate solution, the liquid storage cylinder is made of corrosion-resistant transparent material, and the scale lines further help to mark the remaining amount. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 The preparation flow chart of the present application;

[0019] Figure 2 The molecular structure diagram of the calcium bridging of the present application;

[0020] Figure 3 The molecular structure diagram of the hydrogen bonding of the present application;

[0021] Figure 4 The perspective view of the automatic liquid feeder of the present application;

[0022] Figure 5 The state diagram before liquid feeding of the automatic liquid feeder of the present application;

[0023] Figure 6 The state diagram during liquid feeding of the automatic liquid feeder of the present application;

[0024] Figure 7 The perspective view of the variable liquid passing plate of the present application;

[0025] Figure 8 The connection relationship diagram of the liquid sealing ball and the liquid sealing door of the present application;

[0026] Figure 9 The top view of the variable liquid passing plate of the present application;

[0027] Figure 10 The side view sectional view of the variable liquid passing plate of the present application.

[0028] Explanation of reference numerals in the drawings:

[0029] 1 liquid storage cylinder, 2 liquid feeding hopper, 201 liquid feeding pipe, 202 control cavity, 3 PH value monitoring rod, 4 analyzer, 5 micro electromagnetic iron, 6 dynamic magnetic plate, 7 variable liquid passing plate, 701 through hole, 702 elastic embedded rod, 8 liquid sealing ball, 9 liquid sealing door, 901 magnetic pad. DETAILED DESCRIPTION

[0030] The embodiments will be described in conjunction with the drawings in the specification, and all other embodiments obtained by those skilled in the art based on the embodiments in the present application without creative labor shall fall within the scope of protection of the present application.

[0031] Example 1:

[0032] A preparation method of a composite pectin polysaccharide, please refer toFigure 1 , 2 and Figure 3 , comprising the following preparation steps:

[0033] S1, taking citrus peel residue with water content of 5-12wt%, legume skin residue as raw material, the ratio of the two is legume skin residue: citrus peel residue = 1:1-9, add a certain amount of water, the ratio of water is mixed skin residue: water = 1:15-30, add acid to adjust the PH to 1-3, after stirring, heating reaction for 1-4h, solid-liquid separation is carried out by horizontal screw sedimentation centrifuge to obtain the extract, filter aid is added to filter to obtain the filtrate, ion exchange resin is used for ion exchange of the filtrate, and three-effect concentrator is used for vacuum concentration to obtain the concentrated solution;

[0034] S2, taking organic carboxylic acid salt and water, preparing 50wt% organic carboxylic acid salt solution, wherein the organic carboxylic acid salt is one or more of sodium citrate, potassium citrate, sodium tartrate, potassium tartrate, sodium gluconate and potassium gluconate;

[0035] S3, using the 50wt% carboxylic acid salt solution prepared in S2 step to adjust the PH of the concentrated solution prepared in S1 step to 2.8-5.8, in the process, liquid is added by means of automatic liquid feeder, after the reaction stops, alcohol is added, the concentrated solution is adjusted to 10-50%v / v alcohol concentration by alcohol, stirring reaction is carried out at constant temperature for 0.5-4h, after stirring and standing for a period of time, solid-liquid separation is carried out by plate and frame filter press to obtain wet polysaccharide A;

[0036] S4, taking wet polysaccharide A prepared in S3 step, adding alcohol solution to adjust to 50-90% alcohol concentration, stirring to wash, solid-liquid separation is carried out by plate and frame filter press to obtain wet polysaccharide B, then high temperature vacuum drying, crushing of wet polysaccharide B to obtain the finished product of composite pectin polysaccharide.

[0037] Example 2:

[0038] On the basis of example 1, please refer to Figure 4The automatic liquid feeder in the S3 step comprises a liquid storage cylinder 1 and a liquid adding bucket 2, the liquid storage cylinder 1 is internally provided with an organic carboxylate solution, the liquid storage cylinder 1 is made of corrosion-resistant transparent material, and the outer surface of the liquid storage cylinder 1 is provided with scale lines, so as to facilitate the checking of the remaining amount of the organic carboxylate solution, therefore, the liquid storage cylinder 1 is made of corrosion-resistant transparent material, and the scale lines further help to mark the remaining amount, the middle part of the liquid adding bucket 2 is fixedly embedded with a liquid adding pipe 201 which is in communication with the liquid storage cylinder 1, and the inner wall of the upper end of the liquid adding bucket 2 is provided with a control cavity 202 which is in communication with the liquid adding pipe 201, one side of the lower end of the liquid adding bucket 2 is provided with a PH value monitoring rod 3 (as prior art, the specific model is selected according to actual needs, and will not be described in detail here), and the inside of the liquid adding bucket 2 is provided with an analyzer 4 (as prior art, the specific model is selected according to actual needs, and will not be described in detail here) which is electrically connected with the PH value monitoring rod 3, the analyzer 4 comprises a PH value monitoring module, a PH value setting module and a liquid adding start-stop module, the two sides of the control cavity 202 are both provided with a micro electromagnetic iron 5 (as prior art, the specific model is selected according to actual needs, and will not be described in detail here), and the liquid adding start-stop module is electrically connected with the micro electromagnetic iron 5 through a control processor (the specific connection structure and working principle are the known technology of the person skilled in the art, and will not be described in detail here);

[0039] Please refer to Figure 5 、 6 、7、9 and Figure 10 The two sides of the control cavity 202 are both provided with a dynamic magnetic plate 6 which is repelled by the micro electromagnetic iron 5, and the two dynamic magnetic plates 6 are fixedly connected with a variable liquid passing plate 7, the lower end of the variable liquid passing plate 7 is fixedly connected with a liquid sealing ball 8, and a plurality of through holes 701 which are distributed at equal intervals are formed in the variable liquid passing plate 7, a plurality of elastic embedded rods 702 are fixedly embedded in the inner wall of the variable liquid passing plate 7, and the variable liquid passing plate 7 is made of polyurethane elastic material, the elastic embedded rods 702 make the variable liquid passing plate 7 have a restoring force, so that the variable liquid passing plate 7 can restore to the original shape under the elastic force of the elastic embedded rods 702 after the micro electromagnetic iron 5 is closed, so as to make the liquid sealing ball 8 re-contact with a liquid sealing door 9, thereby closing the downward liquid passing channel of the organic carboxylate solution;

[0040] Please refer to Figure 8 、 10The inner wall of the upper end of the liquid adding pipe 201 is fixedly connected with a sealing liquid door 9 matched with the sealing liquid ball 8, and the sealing liquid door 9 is located below the sealing liquid ball 8. A liquid leakage hole matched with the sealing liquid ball 8 is formed in the sealing liquid door 9, and a magnetic pad 901 magnetically attracted to the sealing liquid ball 8 is fixedly connected to the liquid leakage hole. The magnetic pad 901 is further covered with a security pad, and the security pad is made of silica gel. A layer of security pad is added to the outer layer of the magnetic pad 901 to improve the sealing effect of the sealing liquid ball 8 and the liquid leakage hole, effectively preventing solution leakage. The sealing liquid ball 8 is in close contact with the liquid leakage hole on the sealing liquid door 9, thereby playing a sealing role. The magnetic pad 901 further effectively improves the sealing effect and effectively prevents organic carboxylate solution leakage.

[0041] The working principle of the present application is as follows: the automatic liquid adding device is used to add organic carboxylate solution, effectively avoiding the inaccuracy of manual liquid adding. The automatic liquid adding device is hung in the concentrated solution, and the PH value monitoring rod 3 is immersed in the concentrated solution to monitor the PH value in real time. The PH value setting module sets the PH value to be adjusted. The liquid adding start-stop module first starts the micro electromagnetic iron 5, and the micro electromagnetic iron 5 repels the moving magnetic plate 6, so that the variable liquid passing plate 7 is bent and arched. After the variable liquid passing plate 7 is arched, the sealing liquid ball 8 is separated from the sealing liquid door 9, so that the organic carboxylate solution contained in the liquid storage cylinder 1 flows into the concentrated solution below to adjust the PH value. The PH value monitoring rod 3 monitors the PH value of the concentrated solution in real time. When the monitored PH value reaches the set value, the micro electromagnetic iron 5 is immediately paused by the liquid adding start-stop module. At this time, the variable liquid passing plate 7 restores its original shape under the action of its own elastic force, so that the sealing liquid ball 8 is in close contact with the sealing liquid door 9 again, thereby realizing automatic stopping of liquid adding.

[0042] The above is only the best embodiment adopted by the present application in combination with the current actual demand, but the protection scope of the present application is not limited thereto.

Claims

1. A method for preparing a complex pectic polysaccharide, characterized by, The preparation steps include: S1, taking citrus peel residue and legume skin residue with water content of 5-12wt% as raw materials, the ratio of the two is legume skin residue: citrus peel residue = 1:1-9, add a certain amount of water, the ratio of mixed skin residue: water = 1:15-30, add acid to adjust the PH to 1-3, after stirring and heating reaction for 1-4h, solid-liquid separation is carried out by horizontal screw sedimentation centrifuge to obtain the extraction liquid, filter aid is added to filter to obtain the filtrate, ion exchange resin is used for ion exchange of the filtrate, and then three-effect concentrator is used for vacuum concentration to obtain the concentrated liquid; S2, take organic carboxylic acid salt and water to prepare 50wt% organic carboxylic acid salt solution, wherein the organic carboxylic acid salt is one or more of sodium citrate, potassium citrate, sodium tartrate, potassium tartrate, sodium gluconate and potassium gluconate; S3, adjust the PH of the concentrated liquid prepared in step S1 to 2.8-5.8 by using the 50wt% carboxylic acid salt solution prepared in step S2, and add liquid by means of automatic liquid adding device during the process, then add alcohol after the reaction stops, adjust the concentrated liquid to 10-50%v / v alcohol concentration by alcohol, and stir and react at constant temperature for 0.5-4h, then stir and stand for a period of time, and then solid-liquid separation is carried out by plate and frame filter press to obtain wet polysaccharide A; S4, take wet polysaccharide A prepared in step S3, add alcohol solution to adjust the alcohol concentration to 50-90%, stir and wash, and then solid-liquid separation is carried out by plate and frame filter press to obtain wet polysaccharide B, then high-temperature vacuum drying and crushing are carried out on the wet polysaccharide B to obtain the finished product of composite pectin polysaccharide; The automatic liquid feeder in the S3 step comprises a liquid storage cylinder (1) and a liquid feeding bucket (2), the liquid storage cylinder (1) is internally provided with an organic carboxylate solution, a liquid feeding pipe (201) in communication with the liquid storage cylinder (1) is fixedly embedded in the middle of the liquid feeding bucket (2), a control cavity (202) in communication with the liquid feeding pipe (201) is formed in the inner wall of the upper end of the liquid feeding bucket (2), a PH value monitoring rod (3) is mounted on one side of the lower end of the liquid feeding bucket (2), an analyzer (4) electrically connected with the PH value monitoring rod (3) is mounted in the liquid feeding bucket (2), the analyzer (4) comprises a PH value monitoring module, a PH value setting module and a liquid feeding start-stop module, a micro electromagnetic iron (5) is mounted on both sides of the control cavity (202), the liquid feeding start-stop module is electrically connected with the micro electromagnetic iron (5) through a control processor, a moving magnetic plate (6) repulsive to the micro electromagnetic iron (5) is slidably and sealingly connected on both sides of the control cavity (202), a variable liquid feeding plate (7) is fixedly connected between the two moving magnetic plates (6), a plurality of elastic embedded rods (702) are fixedly embedded in the inner wall of the variable liquid feeding plate (7), the variable liquid feeding plate (7) is made of polyurethane elastic material, a liquid sealing ball (8) is fixedly connected to the middle of the lower end of the variable liquid feeding plate (7), a plurality of through holes (701) are formed in the variable liquid feeding plate (7) at equal intervals, a liquid sealing door (9) matched with the liquid sealing ball (8) is fixedly connected to the inner wall of the upper end of the liquid feeding pipe (201), and the liquid sealing door (9) is located below the liquid sealing ball (8), a liquid leakage hole matched with the liquid sealing ball (8) is formed in the liquid sealing door (9).

2. A process for the preparation of a complex pectic polysaccharide according to claim 1, characterized in that, The liquid leakage hole is fixedly connected with a magnetic pad (901) magnetically attracted to the liquid sealing ball (8).

3. A process for the preparation of a complex pectic polysaccharide according to claim 2, characterized in that, The magnetic pad (901) is further covered with a security pad made of silica gel.

4. The method of claim 1, wherein the complex pectic polysaccharide is prepared by the steps of: The liquid storage cylinder (1) is made of corrosion-resistant transparent material, and the outer surface of the liquid storage cylinder (1) is provided with scale lines. ​

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