CN101392244B - Solid catalyst reaction equipment and running method thereof - Google Patents

Solid catalyst reaction equipment and running method thereof Download PDF

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Publication number
CN101392244B
CN101392244B CN2007101406525A CN200710140652A CN101392244B CN 101392244 B CN101392244 B CN 101392244B CN 2007101406525 A CN2007101406525 A CN 2007101406525A CN 200710140652 A CN200710140652 A CN 200710140652A CN 101392244 B CN101392244 B CN 101392244B
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solid
phase catalyst
face
catalyst
reaction
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CN101392244A (en
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金彩科
王骏
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Bioright Worldwide Co Ltd
BAIRUI GLOBAL Co Ltd
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BAIRUI GLOBAL Co Ltd
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Priority to CN2007101406525A priority Critical patent/CN101392244B/en
Priority to PCT/CN2007/003293 priority patent/WO2009036617A1/en
Publication of CN101392244A publication Critical patent/CN101392244A/en
Priority to HK09108649.9A priority patent/HK1130832A1/en
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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N11/00Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof

Abstract

The invention discloses a solid phase catalyst reactor and a running method thereof. The reactor comprises a reaction vessel and a solid phase catalyst arranged in the reaction vessel. The solid phase catalyst is provided with a first end face, a second end face and a peripheral face extending between the first end face and the second end face, wherein, the peripheral face of the solid phase catalyst is coated with a waterproof membrane. The method comprises the following detailed steps: reaction solution is added into the reaction vessel; the reaction solution is caused to pass through the first end face of the solid phase catalyst and then enters the interior of the reaction vessel and then flows towards the second end face of the solid phase catalyst under the constraint of the waterproof membrane while the reaction solution reacts with the solid phase catalyst and product solution after reaction flows out of the second end face of the solid phase catalyst. The solid phase catalyst reactor and the running method, provided by the invention, can ensure the easy installation and extraction of a reaction column of the solid phase catalyst and can avoid that liquid in the reaction column directly flows out of a column surface and short circuit is caused by deformation/shrinkage of the solid phase catalyst when in running, thereby improving reactive efficiency and running efficiency.

Description

Solid catalyst reaction equipment and operation method thereof
Technical field
The present invention relates to the biological catalyst technical field, particularly relate to a kind of solid catalyst reaction equipment and operation method thereof.
Background technology
Along with development of biology, enzyme is increasingly extensive in industry and other Application for Field as biological catalyst.In above-mentioned application, enzyme or the cell that contains enzyme exist with immobilized form usually.This be because immobilized enzyme or immobilized cell often the specific ionization enzyme is more stable, and be easy to and product separation, be convenient to reclaim and reuse, simultaneously storage and transportation easily.
Usually, immobilized enzyme or immobilized cell are used for suspension reaction with the particulate state form or fill in the container of reaction unit constituting stationary phase, and and flow in the substrate solution reaction between the particle.Yet in the above-mentioned situation, substrate solution generally is difficult to get into granule interior, makes the enzyme molecule that is embedded in the particle deep layer be difficult to participate in catalyzed reaction like this, causes reaction efficiency low.
In order to overcome the above-mentioned shortcoming of particulate state immobilized enzyme or immobilized cell; The inventor has proposed a kind of immobilized enzyme or immobilized cell of novel texture, sees publication number for details and is " CN1982445 ", the denomination of invention one Chinese patent application file for " be used to prepare the carrier of immobilized enzyme or immobilized cell and use this carrier process for fixation ".The three dimensional network structure that this novel immobilized enzyme or immobilized cell have perforate, such structure can increase the touch opportunity of enzyme molecule and substrate solution, increases contact area, and then improves reaction efficiency.
One of application method of the immobilization product of this novel grid structure (immobilized enzyme or immobilized cell); Be that the banded immobilization product of sheet is wound into cylindrical roll axle construction; And directly constitute the reaction cylinder by the cylindrical immobilization product of this spool structure; Perhaps the cylindrical immobilization product of a plurality of this spool structure is piled up up and down and whole formation reaction cylinder, then should be reacted cylinder and place in the reaction vessel.For example; To be " CN1982445 ", denomination of invention just put down in writing such content for the one Chinese patent application file of " be used for prepare the carrier of immobilized enzyme or immobilized cell and use this carrier process for fixation " to publication number: the cylindrical solid enzyme of said reel structure (promptly; The immobilization product) can be used as module; Pile up some such modules up and down to constitute the reaction cylinder, then should react cylinder and fill in the reaction vessel.It with natural shutoff behind solid enzyme piece itself or its surperficial lapping water absorption and swelling, or is tamped with particulate state immobilized enzyme or immobilized cell in gap (hereinafter to be referred as the post jamb gap) between this reaction cylinder and wall of container.Like this, the whole formation reaction of the solid enzyme in container cylinder.
Yet in actual application, there is disadvantage inevitably in the solid catalyst reaction equipment that above-mentioned prior art provided:
One of which; Because it is very close to each other between the solid enzyme piece of formation reaction cylinder and the wall of container of reaction unit; Thereby when taking out the solid enzyme piece; Except needs overcome the weight of enzyme piece self, also need overcome the bigger friction resistance between enzyme piece and the wall of container, make that like this solid enzyme piece is difficult to take out.
They are two years old; Under some industrial conditions, during like the high temperature long-play, deformation/contraction can take place in solid enzyme piece gradually that constitute the reaction cylinder in operational process; Cause and the gap occurs between enzyme piece and the wall of container and cause short circuit; Make the part substrate solution not react like this and just flow away, cause reaction efficiency low, and also reduced the operational efficiency of reaction unit with solid enzyme.So-called short circuit refers to substrate solution in this application and does not react with solid enzyme and just directly flow away from the post jamb gap.
Summary of the invention
For solving the problems of the technologies described above; The invention provides a kind of solid catalyst reaction equipment and operation method thereof; It can make the reaction column that comprises solid-phase catalysts such as immobilized enzyme be easy to pack into and take out; And the liquid that can avoid entering in the reaction column directly flows out and solid-phase catalyst deformation/contractions takes place and cause short circuit at operational process from cylinder, thus raising reaction efficiency and operational efficiency.
For this reason; The invention provides a kind of solid catalyst reaction equipment; Comprise reaction vessel and the solid-phase catalyst that places in the reaction vessel, said solid-phase catalyst has the side face that first end face that reaction solution can flow into, reacted product solution can effusive second end faces and between said first end face and second end face, extended.Wherein, on the side face of said solid-phase catalyst, be enclosed with waterproof membrane.
Solid catalyst reaction equipment provided by the invention also comprises the interface disc of being close to second end face of said solid-phase catalyst.Said interface disc is a cavity structure, has following various piece: the 3rd end face, and have the feed liquor hole slot on it and be close to second end face of said solid-phase catalyst, be used to support said solid-phase catalyst and collect from the liquid of said solid-phase catalyst; The 4th end face, it is provided with water outlet, is used for the liquid in the said interface disc is discharged; The airtight side face that between said the 3rd end face and the 4th end face, extends, itself and said the 4th end face constitute the chamber of receiving fluids jointly.
Wherein, said water outlet is a rising pipe.Preferably, the tube wall that is arranged in the rising pipe pipeline section of said interface disc inner chamber is provided with hole, and the liquid in the interface disc can flow into said rising pipe via described hole.
Wherein, said waterproof membrane extends to said interface disc, and said solid-phase catalyst side face and said interface disc side face are wrapped up together.
Wherein, said waterproof membrane wraps up said side face by means of sticker.Said sticker can comprise hot melt adhesive, surgical adhesive, Carpet Adhesive.
Preferably, said waterproof membrane outside surface is wound with binding tape, in order to tightening said waterproof membrane, thereby said waterproof membrane is wrapped on the said side face more securely.
Wherein, said waterproof membrane is a plastic film.
Wherein, said solid-phase catalyst is column.Said column solid-phase catalyst can be by the banded solid-phase catalyst of sheet around forming; Also can process by the particulate state solid-phase catalyst.
Preferably, said solid-phase catalyst has axis.Like this, said solid-phase catalyst can be reeled around said axis by the banded solid-phase catalyst of sheet and formed.And said axis can be fixed on the central part of said interface disc.
Wherein, Said reaction unit adopts the cis mounting means; That is, down, reaction solution gets into solid-phase catalyst from first end face of the said solid-phase catalyst that is positioned at the top to said solid-phase catalyst at last, said interface disc; And soak into to flow from top to bottom and with the solid-phase catalyst reaction, reacted product solution is collected and is discharged by the interface disc that is positioned at the below.Perhaps; Said reaction unit adopts trans mounting means; That is, said solid-phase catalyst down, said interface disc is last, reaction solution gets into solid-phase catalyst from first end face of the said solid-phase catalyst that is positioned at the below; And soak into to flow from bottom to top and with the solid-phase catalyst reaction, reacted product solution is collected and is discharged by the interface disc that is positioned at the top.
Wherein, said reaction vessel is the post jar.Preferably, said post jar comprises cover, institute
Preferably, the tank skin of said post jar is an interlayer, and the interlayer outer wall is provided with the thermostat(t)ed water gangway, in order in interlayer, to feed thermostat(t)ed water to be incubated.Perhaps, the tank skin of said post jar is an individual layer, and wall is wrapped up in outward with insulating cotton and/or polyurethane foamed material.
The present invention also provides a kind of operation method of solid catalyst reaction equipment; Be specially: in reaction vessel, inject reaction solution; Said reaction solution is got in it via first end face of said solid-phase catalyst; And second end face to said solid-phase catalyst flows under the constraint of said waterproof membrane, reacts with said solid-phase catalyst simultaneously, and reacted product solution flows out from second end face of said solid-phase catalyst.
Wherein, Said reaction solution gets in the reaction vessel from the bottom of said reaction vessel; Gap along between said reaction vessel inwall and the said waterproof membrane rises to said solid-phase catalyst top, gets into said solid-phase catalyst by first end face that is positioned at the top, and flows in said solid-phase catalyst, soaking into downwards under the constraint of said waterproof membrane; React with said solid-phase catalyst simultaneously, reacted product solution flows out from second end face that is positioned at said solid-phase catalyst bottom.Perhaps; Said reaction solution gets in the reaction vessel from said reaction vessel top; Flow down to said solid-phase catalyst bottom along the gap between said reaction vessel inwall and the said waterproof membrane, get into said solid-phase catalyst, and flow in the infiltration that in said solid-phase catalyst, makes progress under the constraint of said waterproof membrane by first end face that is positioned at the bottom; React with said solid-phase catalyst simultaneously, reacted product solution flows out from second end face that is positioned at said solid-phase catalyst top.
Preferably; Said reaction unit also comprises the interface disc of being close to second end face of said solid-phase catalyst; Said interface disc is a cavity structure, has following various piece: promptly, and the 3rd end face that has the feed liquor hole slot on it and be close to second end face of said solid-phase catalyst; It is provided with the 4th end face of water outlet, the airtight side face that between said the 3rd end face and the 4th end face, extends.Wherein, The reaction solution and the said solid-phase catalyst that enter in the said solid-phase catalyst react; Product solution flows out from second end face of said solid-phase catalyst, is collected in the said interface disc via the 3rd end face of said interface disc, then discharges via the water outlet of said interface disc.
Preferably, the wall of container of said reaction vessel is an interlayer, and said operation method also comprises the step of feeding thermostat(t)ed water to be incubated in said interlayer.
With respect to prior art, solid catalyst reaction equipment provided by the invention and operation method thereof have following beneficial effect:
One of which; In solid catalyst reaction equipment provided by the invention; The side face of solid-phase catalyst is enclosed with waterproof membrane, and this waterproof membrane can make the reaction solution in the reaction unit can only enter into the inside of solid-phase catalyst from first end face (that is, opening end face) of solid-phase catalyst; And the reaction solution that enters into solid-phase catalyst inside can not flowed out via this side face; And must be in the solid-phase catalyst internal flow, thereby increased the contact probability of reaction solution and solid-phase catalyst, and then improved the operational efficiency of the reaction efficiency and the reaction unit of solid-phase catalyst.
They are two years old; Solid catalyst reaction equipment provided by the invention is in operational process; The pressure in each site always is slightly larger than the pressure in equal height site in the solid-phase catalyst in the waterproof membrane of parcel solid-phase catalyst and the gap between the wall of container, and this pressure difference forces waterproof membrane to be close to all the time on the side face of solid-phase catalyst.Even if solid-phase catalyst produces deformation/contraction in operational process, this waterproof membrane also can be adjacent to the side face of solid-phase catalyst always under above-mentioned action of pressure, cause short circuit and can between the side face of waterproof membrane and solid-phase catalyst, not form the gap.Like this, the solid-phase catalyst in this reaction unit can react with reaction solution fully, thereby has improved the operational efficiency of the reaction efficiency and the reaction unit of solid-phase catalyst.
They are three years old; Solid catalyst reaction equipment provided by the invention is in operational process, and the waterproof membrane and the gap between the wall of container of parcel solid-phase catalyst are full of reaction solution all the time, and it is inboard (promptly to make that like this waterproof membrane bears from the flexible wall layer simultaneously; In solid-phase catalyst) the pressure that liquid produced; And from the pressure that liquid produced of the flexible wall layer outside (that is, in said gap), thereby; Can not make this flexible wall layer because of only bearing the pressure swelling fracture of a direction, make that the reaction solution in the solid-phase catalyst goes out via disruptive flexible wall laminar flow.Therefore, solid catalyst reaction equipment provided by the invention and operation method thereof can avoid occurring short circuit phenomenon.
They are four years old; Solid catalyst reaction equipment provided by the invention comprises reaction vessel and solid-phase catalyst; The wall of container of this reaction vessel is called the sclerine layer of reaction unit, on the side face of solid-phase catalyst, is enclosed with waterproof membrane, and this waterproof membrane constitutes the flexible wall layer of reaction unit.In this reaction unit operational process, remain between above-mentioned flexible wall layer and the sclerine layer gapped, that is, and the parcel solid-phase catalyst waterproof membrane do not contact with wall of container.Like this; When loading and unloading were enclosed with the solid-phase catalyst of waterproof membrane, solid-phase catalyst and the waterproof membrane that is wrapped in its side face be not because of contacting with wall of container, so just do not exist with the frictional force between the wall of container yet; Like this, only need overcome the gravity of solid-phase catalyst and waterproof membrane self during loading and unloading.Therefore, solid catalyst reaction equipment provided by the invention is easy to loading and unloading.
Description of drawings
Below in conjunction with accompanying drawing, embodiment and application example the present invention is elaborated.
Fig. 1 is the structural representation of the interface disc that adopts of the present invention;
Fig. 2 is the structural representation of the post jar that adopts of the present invention;
Fig. 3 is the structural representation of the solid catalyst reaction equipment of employing cis mounting means provided by the invention;
Fig. 4 is the structural representation of the solid catalyst reaction equipment of the trans mounting means of employing provided by the invention;
Fig. 5 is the structural representation of popular response device in the prior art.
Embodiment
For making those skilled in the art person understand technical scheme of the present invention better, solid catalyst reaction equipment provided by the invention is described in detail below in conjunction with accompanying drawing.
Solid catalyst reaction equipment provided by the invention comprises reaction vessel and the solid-phase catalyst that places in this container.Wherein, solid-phase catalyst can be column, but is not limited thereto.For ease of explanation; Be that example describes hereinafter with the column solid-phase catalyst; And the waterproof membrane of this solid-phase catalyst on being wrapped in its side face (cylinder) be called solid-phase catalyst reaction column or reaction column, and the column solid-phase catalyst that will not be enclosed with waterproof membrane is called naked post of solid-phase catalyst reaction column or the naked post of reaction column.As for waterproof membrane, can be the mantle that plastic film etc. has water-proof function.
Said reaction vessel can be the post jar, but is not limited thereto.The upper end of this post jar can be provided with the cover that can open fully, so that reaction column is packed into and taken out.The jar end and cover all can be provided with fluid inlet, and preferably, these fluid inlets itself are liquid-inlet pipe, perhaps are equipped with liquid-inlet pipe.
How explanation prepares solid-phase catalyst reaction column and the reaction unit that the present invention adopts below.
At first, make the solid-phase catalyst of column spool structure, promptly make the naked post of solid-phase catalyst reaction column.For example, can be " CN1982445 ", denomination of invention according to publication number makes the solid-phase catalyst of cylindric spool structure for the described method of aforementioned one Chinese patent application of " be used to prepare the carrier of immobilized enzyme or immobilized cell and use this carrier process for fixation ".This naked post has the side face that first end face (the open end face of this naked post just) that reaction solution can flow into, reacted product solution can effusive second end faces and between said first end face and second end face, extended.
Then, wrap up in the cylinder of the naked post of this solid-phase catalyst reaction column with the waterproof membrane envelope, thereby obtain the solid-phase catalyst reaction column.
At last, the solid-phase catalyst reaction column that makes is installed in the reaction vessels such as post jar, promptly obtains solid catalyst reaction equipment.
Preferably, the solid-phase catalyst reaction column also comprises and the stacked interface disc of the naked post of solid-phase catalyst reaction column.So-called interface disc refers to column or discous cavity container, is used to collect, hold the liquid from the naked post of reaction column.The inflow face of this interface disc (promptly; Contact and flow into thus that end face of interface disc from the liquid of the naked post of this reaction column with the naked post of reaction column; Also be called the 3rd end face) have mesh or have a multi-ring groove structure of mutual UNICOM, help this mesh or multi-ring groove structure and flow into interface disc from the liquid thereby of the naked post of reaction column; The effluent face of this interface disc (that is, that end face away from the liquid in naked post of reaction column and the interface disc is discharged thus also is called the 4th end face) can be provided with water outlet, and the liquid in the interface disc is discharged via this water outlet.The cylinder of this interface disc is airtight, in order to receiving fluids.More preferably, the shape and size of second end face of the shape and size of the inflow face of this interface disc and the naked post of reaction column are complementary.
The reaction column that has interface disc can be installed in the reaction vessel through following dual mode: cis (that is, interface disc down, solid-phase catalyst is last) with trans (that is, interface disc is descending at last, solid-phase catalyst).When adopting the cis mounting means, reaction solution gets into reaction column from first end face that is positioned at the reaction column top, and soak into downwards flow and with the solid-phase catalyst reaction, product solution imports the interface disc that is positioned at the reaction column bottom, and flows out via the water outlet of interface disc.When adopting trans mounting means, reaction solution gets into reaction column from first end face that is positioned at the reaction column bottom, and upwards soak into flow and with the solid-phase catalyst reaction, product solution imports the interface disc that is positioned at reaction column top, and flows out via the water outlet of interface disc.
In addition, also can be fixed with axis on this interface disc.This axis is the pillar of solid-phase catalyst reaction column, and it can be positioned at the center of this reaction column, and for example, it can be used as the coiling center of the banded solid-phase catalyst of sheet.This axis can run through the two ends of reaction column.
Further the interface disc that is adopted among the present invention is described below in conjunction with accompanying drawing.
See also Fig. 1, the interface disc that the present invention adopted comprises axis 1, interface disc 2 and rising pipe 4.Wherein, interface disc 2 is discoid cavity structure, and its inflow face is the binding face with solid-phase catalyst, and this binding face is processed by the web plate that has mesh, so be called wire side 3; Its effluent face is provided with rising pipe 4.Axis 1 is fixed in the center of the wire side 3 of interface disc 2, the banded solid-phase catalyst of the sheet that is used to reel, for example, solid enzyme.Rising pipe 4 inserts the inner chamber of interface disc 2 and is fixed in the center on interface disc 2 two sides, the i.e. center of inner chamber.The tube wall that is positioned at the part rising pipe 4 of interface disc 2 has four cross-drilled holes that run through 5.In practical application, reaction solution such as substrate solution and the reacted product solution of solid enzyme can be got into the inner chamber of interface disc 2 by the mesh of wire side 3, are pooled to rising pipe 4 through cross-drilled hole 5 again, and flow out thus.
In the present embodiment, all parts of interface disc 2 are processed by stainless steel.Axis 1 is identical with the outside dimension of rising pipe 4, is 20mm; The diameter of interface disc 2 is 145mm.Certainly, this size can optionally enlarge or dwindle.
The quantity that it is pointed out that the cross-drilled hole 5 on the rising pipe 4 is not limited to 4 described in the present embodiment, can for more a plurality of or 4 under.As for the position that is provided with of rising pipe 4, also need not be confined to the center that is arranged on interface disc 2 two sides described in the present embodiment, from the inner chamber of interface disc 2, receive liquid as long as can guarantee rising pipe 4, just can adopt any such position that is provided with.
Below in conjunction with accompanying drawing and with the post jar is that example comes the reaction vessel that is adopted among the present invention is described in detail.
See also Fig. 2, the post jar that is adopted among the present invention comprises tank body 6 and cover 7.The center of cover 7 and tank body 6 bottom surfaces (jar end) all has the rising pipe 4 or the axis 1 that supply the solid-phase catalyst reaction column to stretch out a jar outer hole 8 or a hole 9; Hole 8 or hole 9 are equipped with the lock sealing screw that cooperatively interacts with rising pipe 4 or axis 1; Be used to lock rising pipe 4 or axis 1, and hole 8 or hole 9 are sealed.The cover 7 and jar end, all have the fluid inlet 10 or 11 that communicates with jar chamber.Also be provided with vision slit 12 on the cover 7 and be used to insert the thermowell of TM 13.In the present embodiment, tank skin adopts sandwich structure, can be connected with thermostatical circulating water in the interlayer to be incubated.Tank skin is provided with the access interface 14 of thermostatical circulating water.But in the practical application, the method for tank body insulation also can be adopted in such a way,, outside tank skin, covers the parcel lagging material, like insulating cotton, polyurethane foamed material etc. that is.
In the present embodiment, all parts of post jar are processed by stainless steel, and its principal dimension is: the inner chamber of post jar is high to be 300mm, and intracavity diameter is 170mm.Certainly, this size can optionally enlarge or dwindle.
The preparation of solid-phase catalyst reaction column and naked post thereof is described with specific embodiment below.
The preparation of the naked post of solid-phase catalyst reaction column at first is described.Be appreciated that when the solid-phase catalyst reaction column comprises interface disc so-called naked post refers to, the cylinder that is not enclosed with waterproof membrane that column solid-phase catalyst and interface disc form as a whole; When the solid-phase catalyst reaction column did not comprise interface disc, so-called naked post referred to as previously mentioned, was not enclosed with the formed cylinder of column solid-phase catalyst of waterproof membrane.
The preparation of the naked post of embodiment 1. fixed glucose isomerases
At first; Being " CN1982445 ", denomination of invention according to aforementioned publication number is the described method of one Chinese patent application of " be used to prepare the carrier of immobilized enzyme or immobilized cell and use this carrier process for fixation ", and prepare thick be the sheet band shape fixed glucose isomerase of 5mm, the wide 50mm of being; Then, be the axle center with axis 1 shown in Figure 1, with above-mentioned banded fixed glucose isomerase be wound into thick for 50mm, diameter be the discoid fixed glucose isomerase piece of 150mm; Repeat operating winding, make the discoid fixed glucose isomerase piece of four identical sizes; Again, these four enzyme pieces are close to each other, are piled into the high enzyme piece right cylinder of 200mm, and the wire side 3 of itself and interface disc shown in Figure 12 fitted be close to, promptly obtain the naked post of fixed glucose isomerase.
Next the preparation of solid-phase catalyst reaction column is described.
The preparation method 1 of embodiment 2. fixed glucose isomerase reaction columns
At first, the naked post (that is the naked post of solid-phase catalyst reaction column) for preparing fixed glucose isomerase according to preceding method; Then, at the cylinder of this naked post spraying fusing point be 90 ℃ hot-fusible pressure-sensitive adhesive; Then, paste this naked post of parcel, and will be wrapped in the plastic film that this naked post cylinder is positioned on the interface disc 2 with silicone band and tighten fixing with waterproof membranes such as plastic films.
The preparation method 2 of embodiment 3. fixed glucose isomerase reaction columns
At first, the naked post for preparing fixed glucose isomerase according to preceding method; Then, twine and be covered with banded Carpet Adhesive (this is a kind of gauze base material double faced adhesive tape) at the cylinder of this naked post; Afterwards, paste parcel, and will be wrapped in the plastic film that this naked post cylinder is positioned on the interface disc 2 with silicone band and tighten fixing with waterproof membranes such as plastic films.
The preparation method 3 of embodiment 4. fixed glucose isomerase reaction columns
At first, the naked post for preparing fixed glucose isomerase according to preceding method; Then, paste the cylinder of this naked post of parcel, and will be wrapped in the plastic film that this naked post cylinder is positioned on the interface disc 2 with silicone band and tighten fixing with the plastic film that scribbles hot-fusible pressure-sensitive adhesive.
The preparation method 4 of embodiment 5. fixed glucose isomerase reaction columns
At first, the naked post for preparing fixed glucose isomerase according to preceding method; Then, two-layer with plastic film wrapped at the cylinder of this naked post, the end of top layer plastic film is sticking with hot-fusible pressure-sensitive adhesive envelope, and will be wrapped in the plastic film that this naked post cylinder is positioned on the interface disc 2 with silicone band and tighten fixing.
The preparation method 5 of embodiment 6. fixed glucose isomerase reaction columns
At first, the naked post for preparing fixed glucose isomerase according to preceding method; Then; Be the bigger plastic film sleeve of a diameter on this naked column sleeve; The two ends of plastic film sleeve are individually fixed on the axis 1 that exposes on interface disc 2 and the open end face of this naked post by silicone band; Silicone band on the rotating middle shaft 1 and drive an end torsional direction of plastic film sleeve gently again makes the plastic film sleeve tighten the cylinder of plastic film and this naked post.
The preparation method 6 of embodiment 7. fixed glucose isomerase reaction columns
At first; Being " CN1982445 ", denomination of invention according to publication number is the described method of one Chinese patent application of " be used to prepare the carrier of immobilized enzyme or immobilized cell and use this carrier process for fixation ", and prepare thick be the sheet band shape fixed glucose isomerase of 5mm, the wide 50mm of being; Then, being wound into thick is 150mm discoid (that is, do not have axis and central authorities do not box out crack) for 50mm, diameter; Repeat operating winding, process the discoid fixed glucose isomerase piece of four identical sizes altogether; Afterwards, these four enzyme pieces are close to each other are piled into the high enzyme piece right cylinder of 200mm, and fit with the inflow face of the interface disc that does not have axis and to be close to, thereby make the naked post of fixed glucose isomerase reaction column; Then, paste and wrap up two-layerly, and will be wrapped in the plastic film that this naked post cylinder is positioned on the interface disc with silicone band and tighten fixing with the cylinder that the plastic film that scribbles hot-fusible pressure-sensitive adhesive will this naked post.
It is pointed out that the method for preparing the solid-phase catalyst reaction column described in the previous embodiment 2 to 7, all is to make the naked post of reaction column earlier, then obtains required reaction column with waterproof membrane this naked post of parcel again.Yet in practical application, also can make sleeve with waterproof membrane in advance, then particulate state and/or bulk and/or the banded solid-phase catalyst of sheet etc. filled in this sleeve, thereby obtain required reaction column.This be because, waterproof membrane sleeve softness is yielding, can in reaction unit whole service process, be attached on the solid-phase catalyst side face, this can be avoided defective of the prior art equally, and realizes the object of the invention.
Further it is to be noted; In the aforementioned embodiment; Preparation is with waterproof membrane solid-phase catalyst and interface disc to be wrapped up together when having the reaction column of interface disc, and will be wrapped in the waterproof membrane that this naked post cylinder is positioned on the interface disc with silicone band and tighten fixing.But in practical application, also can solid-phase catalyst and interface disc be wrapped up respectively, or only wrap up solid-phase catalyst, then correspondingly twine silicone band again with waterproof membrane.Certainly, when adopting this mode, interface disc preferably has such structure, that is, its 3rd end face to interface disc chamber sunken inside, and has good transparent performance to reaction solution with respect to its side face.As for the area of this sunk part, can be whole end face, also can be between the area of the area of second end face of the solid-phase catalyst that fits with it and whole end face.And the shape of this sunk part is preferably suitable with the shape of second end face of solid-phase catalyst.
Below, with the structure and the operational process thereof of specific embodiment explanation solid catalyst reaction equipment.
Embodiment 8, the preparation of fixed glucose isomerase double-walled layer reaction unit and operation 1
See also Fig. 3, the structure of the post jar that is adopted in the present embodiment is same as shown in Figure 2, repeats no more at this.Only specify the preparation and the operational process of the solid catalyst reaction equipment in the present embodiment below in conjunction with Fig. 3.
At first, prepare the fixed glucose isomerase reaction column according to the described method of previous embodiment 2-6.
Then, open the cover 7 of post jar, unclamp the central lock screw 15 and 16 at the cover 7 and jar end; Reaction column is installed in the post jar with the cis mode; The rising pipe 4 of reaction column is stretched out, and the central lock screw 16 at the locking jar end from a jar end medium pores 9, the fluid inlet 10 at the bottom of closing jar.
Next, substrate solution (50% (W/V) glucose contains the sal epsom of 1mM, 0.04% S-WAT, and pH is 7.8) is poured into jar in and fill with.Afterwards, in jar, constantly replenish substrate solution, make substrate solution infiltrate reaction column and flow downward to keep the canful state.
Again, when the rising pipe 4 of reaction column has liquid and do not have the bubble outflow, close rising pipe 4; Cover cover 7, let the axis 1 of reaction column stretch out from the medium pore 8 of cover 7; Insert in the thermowell TM 13 and locking, with porthole 12 on cover 7 and the cover 7 and central lock screw 15 lock sealings; Close the fluid inlet 11 on the cover 7, connect the access interface 14 of the thermostatical circulating water of opening 75 ℃.Open the fluid inlet 10 at the rising pipe 4 and jar end, the fluid inlet 10 of substrate solution at the bottom of the jar that will be heated to 75 ℃ with the speed of 200ml/min pumps in the jar continuous service.
Embodiment 9, the preparation of fixed glucose isomerase double-walled layer reaction unit and operation 2
See also Fig. 4, the structure of the post jar that is adopted in the present embodiment is same as shown in Figure 2, repeats no more at this.Only specify the preparation and the operational process of the solid catalyst reaction equipment in the present embodiment below in conjunction with Fig. 4.
At first, prepare the fixed glucose isomerase reaction column according to the described method of previous embodiment 2-6.
Then, open the cover 7 of post jar, unclamp the central lock screw 15 and 16 at the cover 7 and jar end, reaction column is installed in the post jar with trans mode, the axis 1 of reaction column is stretched out from a jar end medium pore 9, and the central lock screw 16 at the locking jar end; Cover cover 7, let the rising pipe 4 of reaction column stretch out from the medium pore 8 of cover 7; Insert in the thermowell TM 13 and locking, with porthole 12 lock sealings on cover 7 and the cover 7; Fluid inlet 10 at the bottom of closing jar connects and opens 75 ℃ of thermostatical circulating waters.
Next, the fluid inlet 11 of 75 ℃ substrate solution (among its composition and the embodiment 8 identical) from cover pumped in the jar, during to rising pipe 4 flowing liquids of reaction column, unclamp porthole 12 exhausts with the speed of 200ml/min.When porthole 12 has liquid to flow out, locking porthole 12.With above-mentioned state continuance operation.
Embodiment 10, the preparation of fixed glucose isomerase double-walled layer reaction unit and operation 3
The structure of the post jar that is adopted in the present embodiment is same as shown in Figure 2, and operational process and previous embodiment 9 are similar, repeat no more at this.
Present embodiment and embodiment 9 have following difference: one of which; The fixed glucose isomerase reaction column that is adopted in the present embodiment is according to previous embodiment 7 described method preparations; In other words, the fixed glucose isomerase reaction column that is adopted in the present embodiment does not have axis; Its two because the reaction column in the present embodiment does not have axis, so need the medium pore at the bottom of the post jar jar 9 sealing for example, can be adopted solid minor axis shutoff.
Embodiment 11, the preparation and the operation of fixed glucose isomerase popular response device.
Is example below in conjunction with Fig. 5 with fixed glucose isomerase popular response device, and the preparation and the operation of existing apparatus are described, to further specify the beneficial effect that solid catalyst reaction equipment provided by the invention is had by comparison.
The preparation process and the structure thereof of the solid-phase catalyst reaction column that is adopted in the existing apparatus are following:
At first, being " CN1982445 ", denomination of invention according to publication number prepares thick be 5mm, wide sheet band shape fixed glucose isomerase as 50mm for the one Chinese patent application of " be used to prepare the carrier of immobilized enzyme or immobilized cell and use this carrier process for fixation ".
Then, be that the stainless steel solid axle of 20mm is the axle center with the diameter, the banded fixed glucose isomerase of sheet is wound into 50mm is thick, diameter is the discoid of 170mm.Fix its terminal stickup of reeling with the small amount of thermal melten gel.
Again, repeat operating winding, process the discoid fixed glucose isomerase piece of four identical sizes altogether.These four enzyme pieces are close to each other are piled into the high enzyme piece right cylinder 18 of 200mm, that is, and solid-phase catalyst reaction column 18.
The structure of the post jar that is adopted in the present embodiment is same as shown in Figure 2, repeats no more at this.
The operational process of popular response device only is described below.
At first, the enzyme piece right cylinder that makes 18 is inserted in the post jars, the middle position in being located at jar, and make the axis 17 of enzyme piece right cylinder 18 pass the medium pore 8 and 9 at the cover 7 and jar end, lock the lock screw 15 and 16 of cover 7 and medium pore 8 and 9.
Then, connect the access interface 14 of opening 75 ℃ of thermostatical circulating waters; And 75 ℃ the substrate solution fluid inlet 10 at the bottom of the jar is pumped into tank body with the speed of 200ml/min, until fluid inlet 11 flowing liquids of cover 7.With above-mentioned state continuance operation.
Next, the test-results of more above-mentioned each embodiment.
Implement test according to the foregoing description 8~11 described methods, regularly collect the elute of reaction column every day.Being " CN1982445 ", denomination of invention according to publication number measures the fructose transformation efficiency of substrate solution for " be used to prepare the carrier of immobilized enzyme or immobilized cell and use this carrier process for fixation " described method; By the transformation period that transformation efficiency attenuation degree in time calculates solid enzyme among each embodiment, the result is following:
The reaction column preparation method Operation method Double-walled layer structure Transformation period
Embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 11 Embodiment 8 embodiment 8 embodiment 9 embodiment 9 embodiment 9 embodiment 10 embodiment 11 Whether be 17 days 16 days 18 days 19 days 19 days 19 days 4 days
Can find out from last table, adopt solid catalyst reaction equipment provided by the invention, the transformation period of the solid enzyme in it is 16~19 days; Do not adopt this reaction unit, the transformation period of the solid enzyme in it is 4 days.
The shape of the solid-phase catalyst reaction column that it is pointed out that among the present invention to be adopted can be not limited to cylindrical described in the previous embodiment, also can wait the cylinder of other shapes for prism, can certainly be other shapes of non-cylinder.Similarly, the axis of reaction column also can wait the cylinder of other shapes for prism.In addition, the shape of interface disc also is not limited to the disc-shape described in the previous embodiment, is the cylinder of shapes such as Polygons but can adopt end face.Preferably, the shape of interface disc end face and size are complementary with end face with the column solid-phase catalyst of its applying.As for the quantity of the reaction column rising pipe that is adopted among the present invention, can be not limited to described in the previous embodiment, also can be for a plurality of, so just require the cover of post jar or the quantity of the water outlet that is provided with can not be less than the quantity of rising pipe at jar the end
The reaction vessel that further it is pointed out that among the present invention to be adopted can be not limited to the post jar described in the previous embodiment, can be any suitable container.In addition, the modes of emplacement of the post jar that is adopted among the present invention can be not limited to the vertical type described in the previous embodiment, but can adopt any form that can realize the object of the invention.
It is understandable that above embodiment only is the illustrative embodiments that adopts for principle of the present invention is described, yet the present invention is not limited thereto.For the one of ordinary skilled in the art, under the situation that does not break away from spirit of the present invention and essence, can make various modification and improvement, these modification also are regarded as protection scope of the present invention with improving.

Claims (27)

1. solid catalyst reaction equipment; Comprise reaction vessel and the solid-phase catalyst that places in the reaction vessel; Said solid-phase catalyst has the side face that first end face that reaction solution can flow into, reacted product solution can effusive second end faces and between said first end face and second end face, extended; It is characterized in that, on the side face of said solid-phase catalyst, be enclosed with waterproof membrane.
2. solid catalyst reaction equipment according to claim 1 is characterized in that, also comprises the interface disc of being close to second end face of said solid-phase catalyst, and said interface disc is a cavity structure, has following various piece:
The 3rd end face has the feed liquor hole slot and is close to second end face of said solid-phase catalyst on it, be used to support said solid-phase catalyst and collect from the liquid of said solid-phase catalyst;
The 4th end face, it is provided with water outlet, is used for the liquid in the said interface disc is discharged;
The airtight side face that between said the 3rd end face and the 4th end face, extends, itself and said the 4th end face constitute the chamber of receiving fluids jointly.
3. solid catalyst reaction equipment according to claim 2 is characterized in that, said water outlet is a rising pipe.
4. solid catalyst reaction equipment according to claim 3 is characterized in that, the tube wall that is arranged in the rising pipe pipeline section of said interface disc inner chamber is provided with hole, and the liquid in the interface disc can flow into said rising pipe via described hole.
5. solid catalyst reaction equipment according to claim 2 is characterized in that said waterproof membrane extends to said interface disc, and said solid-phase catalyst side face and said interface disc side face are wrapped up together.
6. according to claim 1 or 5 described solid catalyst reaction equipments, it is characterized in that said waterproof membrane wraps up said side face by means of sticker.
7. solid catalyst reaction equipment according to claim 6 is characterized in that said sticker comprises hot melt adhesive, surgical adhesive, Carpet Adhesive.
8. solid catalyst reaction equipment according to claim 6 is characterized in that, said waterproof membrane outside surface is wound with binding tape, in order to tightening said waterproof membrane, thereby said waterproof membrane is wrapped on the said side face more securely.
9. solid catalyst reaction equipment according to claim 1 is characterized in that, said waterproof membrane is a plastic film.
10. solid catalyst reaction equipment according to claim 1 is characterized in that said solid-phase catalyst is column.
11. solid catalyst reaction equipment according to claim 10 is characterized in that, said column solid-phase catalyst is reeled by the banded solid-phase catalyst of sheet and is formed.
12. solid catalyst reaction equipment according to claim 10 is characterized in that, said column solid-phase catalyst is processed by the particulate state solid-phase catalyst.
13. solid catalyst reaction equipment according to claim 1 and 2 is characterized in that, said solid-phase catalyst has axis.
14. solid catalyst reaction equipment according to claim 13 is characterized in that, said solid-phase catalyst is reeled around said axis by the banded solid-phase catalyst of sheet and is formed.
15. solid catalyst reaction equipment according to claim 13 is characterized in that, said axis is fixed on the central part of said interface disc.
16. solid catalyst reaction equipment according to claim 2; It is characterized in that said reaction unit adopts the cis mounting means, promptly; Said solid-phase catalyst is descending at last, said interface disc; Reaction solution gets into solid-phase catalyst from first end face of the said solid-phase catalyst that is positioned at the top, and soak into from top to bottom flow and with the solid-phase catalyst reaction, reacted product solution is collected and is discharged by the interface disc that is positioned at the below.
17. solid catalyst reaction equipment according to claim 2; It is characterized in that said reaction unit adopts trans mounting means, promptly; Said solid-phase catalyst down, said interface disc is last; Reaction solution gets into solid-phase catalyst from first end face of the said solid-phase catalyst that is positioned at the below, and soak into from bottom to top flow and with the solid-phase catalyst reaction, reacted product solution is collected and is discharged by the interface disc that is positioned at the top.
18. solid catalyst reaction equipment according to claim 1 is characterized in that, said reaction vessel is the post jar.
19. solid catalyst reaction equipment according to claim 18 is characterized in that, said post jar comprises cover, and a said cover and/or a jar end are provided with fluid inlet, and reaction solution is in said fluid inlet enters into said post jar.
20. solid catalyst reaction equipment according to claim 19 is characterized in that, a said cover and/or a jar end, are provided with medium pore, stretch out for the axis of said solid-phase catalyst and/or the rising pipe of interface disc.
21. according to any described solid catalyst reaction equipment in the claim 18 to 20, it is characterized in that the tank skin of said post jar is an interlayer, the interlayer outer wall is provided with the thermostat(t)ed water gangway, in order in interlayer, to feed thermostat(t)ed water to be incubated.
22. according to any described solid catalyst reaction equipment in the claim 18 to 20, it is characterized in that the tank skin of said post jar is an individual layer, wall is wrapped up in outward with insulating cotton and/or polyurethane foamed material.
23. the operation method of solid catalyst reaction equipment as claimed in claim 1; It is characterized in that; In reaction vessel, inject reaction solution, said reaction solution is got in it via first end face of said solid-phase catalyst, and second end face to said solid-phase catalyst flows under the constraint of said waterproof membrane; React with said solid-phase catalyst simultaneously, reacted product solution flows out from second end face of said solid-phase catalyst.
24. the operation method of solid catalyst reaction equipment according to claim 23; It is characterized in that; Said reaction solution gets in the reaction vessel from the bottom of said reaction vessel; Gap along between said reaction vessel inwall and the said waterproof membrane rises to said solid-phase catalyst top, gets into said solid-phase catalyst by first end face that is positioned at the top, and flows in said solid-phase catalyst, soaking into downwards under the constraint of said waterproof membrane; React with said solid-phase catalyst simultaneously, reacted product solution flows out from second end face that is positioned at said solid-phase catalyst bottom.
25. the operation method of solid catalyst reaction equipment according to claim 23; It is characterized in that; Said reaction solution gets in the reaction vessel from said reaction vessel top; Flow down to said solid-phase catalyst bottom along the gap between said reaction vessel inwall and the said waterproof membrane, get into said solid-phase catalyst, and flow in the infiltration that in said solid-phase catalyst, makes progress under the constraint of said waterproof membrane by first end face that is positioned at the bottom; React with said solid-phase catalyst simultaneously, reacted product solution flows out from second end face that is positioned at said solid-phase catalyst top.
26. operation method according to the described solid catalyst reaction equipment in any top in the claim 23 to 25; It is characterized in that; Said reaction unit also comprises the interface disc of being close to second end face of said solid-phase catalyst, and said interface disc is a cavity structure, has following various piece: promptly; The 3rd end face that has the feed liquor hole slot on it and be close to second end face of said solid-phase catalyst; It is provided with the 4th end face of water outlet, the airtight side face that between said the 3rd end face and the 4th end face, extends, wherein
The reaction solution and the said solid-phase catalyst that enter in the said solid-phase catalyst react; Product solution flows out from second end face of said solid-phase catalyst; Be collected in the said interface disc via the 3rd end face of said interface disc, then discharge via the water outlet of said interface disc.
27. the operation method of solid catalyst reaction equipment according to claim 23 is characterized in that, the wall of container of said reaction vessel is an interlayer, and said operation method also comprises the step of feeding thermostat(t)ed water to be incubated in said interlayer.
CN2007101406525A 2007-09-21 2007-09-21 Solid catalyst reaction equipment and running method thereof Active CN101392244B (en)

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CN2007101406525A CN101392244B (en) 2007-09-21 2007-09-21 Solid catalyst reaction equipment and running method thereof
PCT/CN2007/003293 WO2009036617A1 (en) 2007-09-21 2007-11-21 A solid catalyst reactive arrangement and its running method
HK09108649.9A HK1130832A1 (en) 2007-09-21 2009-09-22 A solid catalyst reactive arrangement and operating method thereof

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CN102116666A (en) * 2011-01-05 2011-07-06 丹东科泰仪器仪表有限公司 Constant-temperature sonic nozzle process gas flow calibration facility and constant-temperature stagnation vessel
CN105073241B (en) * 2013-03-14 2017-10-03 艾迪·陈 The electrical activation method and apparatus of catalyst
CN108642035B (en) * 2018-05-08 2022-03-25 江苏理工学院 Method for preparing NADPH (nicotinamide adenine dinucleotide) under catalysis of GDH (GDH) immobilized on silica gel

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DE19822050A1 (en) * 1998-05-16 1999-11-18 Forschungszentrum Juelich Gmbh Chemical or biological reactions on surface of particles, retained in container permeable to reaction fluid, especially for growing cells
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