A kind of method that 1,5- pentanediamines are extracted from the solution system of the salt of pentanediamine containing 1,5-
Technical field
The present invention relates to chemical products separation, purification art, and in particular to one kind is from containing 1,5- pentanediamine salt
Solution system in extract 1,5- pentanediamines method.
Background technology
Pentanediamine (i.e. 1,5- pentanediamines, 1,5- 1,5-DAPs, cadaverine etc.) is a kind of important polymerization
Thing monomer.Set out from 1,5- pentanediamines, serial polyamide, such as polyamide 56, polyamide 510 can be synthesized
Deng, or the product such as polyesteramide, it is widely used in the neck such as weaving, electronic apparatus, plant equipment, automobile
Domain.
The production of 1,5- pentanediamine and purifying patent, can enumerate following report:
In patent CN101981202A, pentanediamine is produced by direct fermentation.Zymotic fluid is at 103 DEG C
Under, flow back 5 hours, the accessory substance in cracking zymotic fluid is repeatedly extracted with butanol, evaporated organic afterwards
Solvent obtains pentanediamine product.In the technique of pentanediamine is extracted using organic solvent, because of pentanediamine characteristic
Influence, commonly use polar organic solvent extraction.Using organic solvents such as chloroform or butanol in such technique,
It is inevitable in extraction process to have solvent volatilization, cause environmental pollution, and must have follow-up molten
Agent recycling step, adds extraction cost.
In patent CN200980121108, pentanediamine enzyme reaction solution is organic with UF12000 molecular weight
Film process, to reduce trifunctional organic matter in reaction solution.Pentanediamine solution after processing is heated to 100
Pentanediamine carbonate is decomposed more than DEG C, pentanediamine is then distilled and obtains product.The decomposition of carbonate need compared with
High temperature and long-time heating, and it cannot be guaranteed that the whole of carbonate decompose, to rectification process and production
Quality can be impacted.The method is only applicable to from pentanediamine carbonate separate 1,5- pentanediamines,
Applicability is very limited system.
Patent CN101970393A replaces extraction by the way of liquid feeding state alkali and nanofiltration, to improve penta 2
The rate of recovery of amine.But the inapplicable situation with the presence of a large amount of solid impurities of the use of nanofiltration, when containing in system
In the presence of having solid impurity or a big molecular impurities such as a large amount of thalline, inorganic salts precipitation, if used
Nanofiltration, then must first pass through micro-filtration even ultrafiltration before nanofiltration and carry out pre-filtering, otherwise nanofiltration flux is very
It is low and be easily blocked, time consumption and energy consumption, and damage the service life of NF membrane.Moreover, this method base
It is only applicable to add the situation of dissolubility alkali or aqueous slkali in sheet.If being put using sodium hydroxide or potassium hydroxide
Change and there is the salt such as a large amount of sodium sulphate or sodium chloride, potassium sulfate in pentanediamine salt, final solution system,
The evaporation yield of pentanediamine can be influenceed by being separated out in later stage distillation.
The content of the invention
For overcome the purifying of existing pentanediamine, complex process present in extraction process, it is with high costs, reclaim
The relatively low defect of rate, is carried it is an object of the invention to provide one kind from the solution system of the pentanediamine salt containing 1,5-
The method for taking 1,5- pentanediamines.
The side that 1,5- pentanediamines are extracted from the solution system of the salt of pentanediamine containing 1,5- that the present invention is provided
Method, comprises the following steps:
S1:Alkaline matter is added into the solution system of the salt of pentanediamine containing 1,5- to be formed containing free
The solution system of state 1,5- pentanediamines;
S2:Solution system obtained by step S1 is carried out in vacuum scraper drying device to distill/evaporate,
The vacuum of the distillation/evaporation is -0.15~-0.05MPa, and temperature is 120~250 DEG C.
In the method that the present invention is provided, vacuum preferably -0.12~-0.05MPa of the distillation/evaporation, more
Preferably -0.095~-0.09MPa;And/or, preferably 150~230 DEG C of the temperature of the distillation/evaporation, more
Preferably 170~210 DEG C, more preferably 190~200 DEG C.
In the method that the present invention is provided, 1,5- penta 2 is included in the solution system for containing 1,5- pentanediamine salt
One or more in sulfate, carbonate, phosphate, hydrochloride and the dicarboxylate of amine;The 1,5-
Concentration range of the pentanediamine salt in the solution system is preferably 5wt%~35wt%, and more preferably 20
Wt%~30wt%.
In the method that the present invention is provided, 1,5- penta 2 is included in the solution system for containing 1,5- pentanediamine salt
One or more in sulfate, carbonate and the phosphate of amine, its mole is not less than the solution body
The 70% of 1,5- pentanediamines salt integral molar quantity, preferably not lower than 75%, are more preferably not less than in system
80%, more preferably it is not less than 85%, most desirably not less than 90%.Above-mentioned mole is represented:When
Contain sulfate, the carbonate of single 1,5- pentanediamines in the solution system of the salt of pentanediamine containing 1,5-
During with any of phosphate, in sulfate, carbonate and the phosphate of this single 1,5- pentanediamine
A kind of ratio for accounting for 1,5- pentanediamines salt integral molar quantity in the solution system;Or represent, containing work as
Sulfate containing 1,5- pentanediamines, carbonate and phosphoric acid in the solution system of the salt of pentanediamine containing 1,5-
During two or more in salt, the sulfate of 1,5- pentanediamine, carbonate and phosphatic and account for institute
State the ratio of 1,5- pentanediamines salt integral molar quantity in solution system.
In the method that the present invention is provided, the alkaline matter preferably includes sodium hydroxide, potassium hydroxide, ammonia
One or more in water, calcium hydroxide, magnesium hydroxide, calcium oxide and magnesia.The alkaline matter
Consumption be that the 1,5- pentanediamines in the solution system of the salt of pentanediamine containing 1,5- can be made to form trip completely
1~1.5 times of the minimum amount of amorph, preferably 1~1.2 times, more preferably 1~1.1 times, wherein, one
The mol ratio of valency cation alkaline matter and 1,5- pentanediamine salt is (2~3):1, be preferably (2~2.4):
1, more preferably (2~2.2):1;The mol ratio of bivalent cation alkaline matter and 1,5- pentanediamine salt is
(1~1.5):1, be preferably (1~1.2):1, more preferably (1~1.1):1.
In the method that the present invention is provided, when the solution system for containing 1,5- pentanediamine salt includes 1,5- penta
During one or more in sulfate, carbonate and the phosphate of diamines, the alkaline matter accordingly includes
Calcium hydroxide, magnesium hydroxide, the one or more of calcium oxide and magnesia.
In the method that the present invention is provided, in step S1, temperature when adding the alkaline matter is preferably
20~90 DEG C, more preferably 20~65 DEG C, be further preferably 25~45 DEG C, more preferably 30~40 DEG C.
In the method that the present invention is provided, the solution system for containing 1,5- pentanediamine salt is preferably to contain 1,5- penta
The aqueous solution, 1,5- pentanediamine enzymatic conversion liquid or the 1,5- pentanediamine zymotic fluids of diamine salts.
In the method that the present invention is provided, also include the solution body obtained by step S1 before the step S2
It is the step of concentration.
In the method that the present invention is provided, preferably also include before the step S1 degerming and/or de-
The pre-treatment step of color.
In the method that the present invention is provided, rotating speed preferably 0.05~15rpm of the vacuum scraper drying device,
It is further preferably 0.1~10rpm, more preferably more preferably 0.2~5rpm, 0.5~1rpm.
In the method that the present invention is provided, the charging rate preferably 5~50 of the vacuum scraper drying device
kg/m2/ h, more preferably 10~40kg/m2/ h, is further preferably 18~30kg/m2/h。
In the method that the present invention is provided, the thickness of appended thin layer is preferred on the vacuum scraper drying device
0.4~2mm, more preferably 0.5~1.5mm, are further preferably 0.8~1mm.
In the method that the present invention is provided, the vacuum scraper drying device includes vacuum plant, set
Rotary drum body, feed liquid disk, scraper among the vacuum plant, and be arranged under the scraper
The material residue collection device of side, the rotary drum body is driven by rotary shaft and rotated, positioned at the feed liquid
The solution system obtained by step S1 in disk forms thin layer after being contacted with the rotary drum body, through S2
Step, then scraped material residue by the scraper, and collect and discharge through the material residue collection device.
In the method that the present invention is provided, the material residue collection device preferably includes material residue funnel and material
The entrance for controlling material residue to enter and discharge is provided with slag collection bucket, the material residue collection bucket
Valve and outlet valve, and for being passed through the pressure-regulating valve of air and vacuum conditions for vacuumizing
Valve.
In the method that the present invention is provided, the rotary drum body preferably includes inner cylinder and outer barrel, described interior
The deflector for diversion heating medium is provided between cylinder and outer barrel.
In the method that the present invention is provided, the deflector is preferably distributed in the shape of a spiral.
In the method that the present invention is provided, agitating device preferably is additionally provided with the vacuum plant, is used
In stirring the solution system in the feed liquid disk, it connects through the rotary shaft with the rotary shaft
Drive.
In the method that the present invention is provided, the draw ratio preferably 0.6~2.6 of the rotary drum body, more preferably
It is further preferably 1.0~1.5 for 0.8~2.
In current 1,5- pentanediamines production, the intermediate product pentanediamine salt component of formation has diversity (often
Seeing has sulfate, carbonate, phosphate, hydrochloride, dicarboxylate etc.), when the alkaline matter system of addition
During for free pentanediamine, because the species of salt is complicated, various reluctant situations are also brought.
For example, when pentanediamine salt is generally hydrochloride, carboxylate, adding sodium hydroxide, potassium hydroxide etc.
Readily soluble inorganic salts are produced during highly basic, it is smaller on follow-up distillation/evaporation process influence, but when in pentanediamine salt
During containing sulfate, carbonate, phosphate, prior art is also many using addition sodium hydroxide, hydrogen-oxygen
Change the highly basic such as potassium, but inorganic salts crystallization is easily produced in follow-up distillation/evaporation process, influence distillation/
Evaporation effect and pentanediamine yield, and when using alkali such as calcium hydroxide, magnesium hydroxides, prior art
Then generally believe that it is difficult to pentanediamine reactant salt completely, and a large amount of inorganic salts precipitations can be produced.Remove
The influence of inorganic salts is gone, the composition of the solution system of the pentanediamine salt containing 1,5- in itself also possesses complexity, its
Include the organic impurities such as albumen, sugar, the pigment of substantial amounts of thalline, fermentation or biotransformation residual.
Based on afore-mentioned, as carried out using conventional distillation still in follow-up distillation/evaporation step, distillation/
Thick kettle base solution can be formed in evaporation process after moisture evaporation, sticky kettle base solution, which can have a strong impact on, to be stirred
Mix and stir in heat and mass efficiency, kettle base solution also can entrainment portions 1,5- pentanediamines, cause final distillation/
Evaporation yield is relatively low, and discarded object is also very difficult after distillation/evaporation, and manufacture can be industrially significantly greatly increased
Cost and environmental pressure.
For these situations of pentanediamine distillation/evaporation process, existing reply technology is that selection highly basic is made mostly
For alkaline matter and pentanediamine reactant salt, and increase the separation of solid and liquid process steps such as filtering, to mitigate
The influence of solid in system for distillation/evaporation process.But, do not set about from evaporation equipment
Solution, is still limited to conventional distillation/evaporation equipment, and the yield of pentanediamine is difficult to reach preferably
State.It was found by the inventors of the present invention that in the evaporation process of pentanediamine, the evaporation that routine techniques is used
There is major defect in kettle, conventional evaporating kettle is by solution to be evaporated in terms of heat transfer, evaporation mode
System is placed in one, and it is integrally heated to evaporate pentanediamine, due to solution system to be evaporated
It is more, wherein there is solid in addition, being easily caused heat can not be delivered to inside solution system, so that
The evaporation of pentanediamine is reduced, is also easy to make the solid in solution system to produce caking, free penta 2
Amine is wrapped in wherein, has had a strong impact on ultimate yield, therefore, in industrialized pentanediamine production process
In, these are all the key factors for restricting pentanediamine evaporation efficiency.Vacuum scraper drying device is by steaming
Shampoo point or solvent obtain dry product, in evaporation process, and material to be evaporated is in heating cylinder wall
Upper formation thin layer, heating is thorough, it is not easy to produces thick or cake mass, is applicable to pentanediamine molten
The complicated ingredient of liquid system, it is different from normal usage, the gas of discharge need to be collected when being extracted for pentanediamine,
The aqueous solution containing pentanediamine can be obtained after cooling.The material residue produced after evaporation is fluffy, it is easy to discharged
And be easy to carry out industrial waste processing.
Present inventor has further discovered that, it can be entered as distillation/evaporation equipment using vacuum scraper drying device
One step simplifies the extraction process of whole pentanediamine.As it was previously stated, when in pentanediamine salt contain more sulfuric acid
During the salt such as salt, carbonate, phosphate, the highly basic of more options addition such as sodium hydroxide is reacted, because
To have been generally acknowledged that addition weak base or slightly solubility alkali are difficult to make pentanediamine reactant salt completely, what is remained in system consolidates
The solid such as body alkali and the slightly solubility inorganic salts of generation precipitation can influence the yield of pentanediamine.Such
Under Technologies And Conceptions, prior art is more using addition water soluble alkali such as sodium hydroxide, hydrogen-oxygen in the selection of alkali
Change weak solution of potassium solution or slightly solubility alkali etc. to avoid the conversion process of pentanediamine salt from having solid generation, or
Person strengthens solid-liquid separation process after adding alkali to react, to avoid influence of the solid precipitation to evaporation process.But
It is, it was found by the inventors of the present invention that it is different from the understanding of prior art, addition slightly solubility alkali such as calcium oxide,
Calcium hydroxide, magnesium hydroxide etc., make it generate the inorganic salts of slightly solubility precipitation, precipitation in solution system
Generation promoted the continued dissolution process of above-mentioned slightly solubility alkali in the solution, so as to hold pentanediamine salt
Continuously, stably converted to pentanediamine, the conversion ratio of pentanediamine is substantially increased on the contrary, used while working as
When vacuum scraper drying device is as distillation/evaporation equipment, even if there is the solid impurities such as thalline in solution system
Or in the presence of having a solid-solid inorganic salt sediment, extracting method of the invention can also obtain preferable receipts
The pentanediamine of rate, and the solid-liquid separation step such as filter without carrying out in distillation/evaporation process, therefore not
Seldom go out, extracting method applicability of the invention is wide and can simplify whole extraction process.
The extracting method of the present invention can be directed to the various salt types of 1,5- pentanediamines, and it is various to be applicable addition
Alkaline matter, applicability is stronger, have more cost competitiveness, and evaporation is used as using vacuum scraper drying device
Equipment, greatly improves the ultimate yield of pentanediamine, and solid will not produce influence to distillation/evaporation process,
Directly it is evaporated without separation of solid and liquid after adding alkaline matter, simplifies processing step.Sum it up,
Extracting method that the present invention is provided is practical, technique is simple, easy to operate, can obviously reduce whole work
Skill flow cost of material and running cost, and can obtain the rate of recovery of preferable 1,5- pentanediamines.
Brief description of the drawings
Fig. 1 is the vacuum plant and its schematic diagram of internal structure of the vacuum scraper drying device of the present invention;
Fig. 2 is the schematic diagram of the material residue collection device of the vacuum scraper drying device of the present invention;
Fig. 3 is the schematic diagram of the part-structure in the vacuum scraper drying device vacuum plant of the present invention;
Wherein, description of reference numerals is as follows:1st, rotary drum body;101st, inner cylinder;102nd, outer barrel;103、
Deflector;2nd, rotary shaft;3rd, feed liquid disk;4th, scraper;5th, vacuum plant;501st, gas vent;
6th, power set;7th, material residue collection device;701st, material residue funnel;702nd, material residue collection bucket;703、
Material residue passage;704th, inlet valve;705th, outlet valve;706th, vacuum breaker;707th, pressure is adjusted
Valve;8th, agitating device;801st, agitator;802nd, stirrer gear is roused;803rd, gear is stirred.
Embodiment
1,5- pentanediamines are extracted from the solution system of the salt of pentanediamine containing 1,5- the invention provides a kind of
Method, this method comprises the following steps:
S1:Alkaline matter is added into the solution system of the salt of pentanediamine containing 1,5- to be formed containing free
The solution system of state 1,5- pentanediamines;
S2:Solution system obtained by step S1 is carried out in vacuum scraper drying device to distill/evaporate,
The vacuum of the distillation/evaporation is -0.15~-0.05MPa, and temperature is 120~250 DEG C.
At present, industrially prepare and use bioanalysis more 1,5- pentanediamines, therefore according to the present invention's
In one embodiment of method, the solution system of the pentanediamine salt containing 1,5- can be biological fermentation process
The zymotic fluid of the pentanediamine salt Han 1,5- of production, or enzymatic conversion liquid or lysine salt are in lysine decarboxylation
In the presence of enzyme (LDC), react obtained pentanediamine salt enzymatic conversion liquid, or can also be containing
The aqueous solution of 1,5- pentanediamine salt.The acquisition of industrial pentanediamine salting liquid is general to be turned by fermentation or enzyme
Chemical industry skill is obtained.At the end of fermentation or enzymatic conversion, aqueous solution pH is normally close to neutrality, pentanediamine
It is present in a salt form in the aqueous solution.Enzymatic conversion liquid or zymotic fluid of the present invention can be contained
There is the stoste without any processing of thalline, the present invention is not important to zymotic fluid or enzymatic conversion liquid
Ask.One of technique effect of the present invention be handle the fermentation for containing largely solvable/insoluble impurity/
Enzymatic conversion stoste, can omit step before degerming removal of impurities in traditional handicraft etc. is separated, but this is not limited
Make the solution for containing 1,5- pentanediamines and be only fermentation/enzymatic conversion stoste, may infer that and do not contain/part
1,5- pentanediamines solution system containing solvable/insoluble impurity does not interfere with the effect of the present invention certainly yet
Really, therefore the solution system that contains 1,5- pentanediamines can also be the solution obtained after further processing
System (general designation treatment fluid), such as uses ceramic membrane or ultrafiltration membrance filter thalline and albumen macromolecular complex
The settled solution obtained after matter, or the solution that simple filtration is obtained, or the clear liquid that centrifugation is obtained, or
With the solution obtained after decolorization and impurity removal by active carbon or can also be pentanediamine be dissolved in water formation penta
Two amine aqueous solutions.During these, insoluble impurities or soluble impurity can be removed, and 1,5-
Pentanediamine salt is preserved among solution system.In addition, enzymatic conversion liquid or zymotic fluid, or processing
Treatment fluid afterwards can also be concentrated further, and the method for concentration can use any applicable existing skill
Art, such as evaporation, air-distillation, vacuum distillation, counter-infiltration.That is, described contains 1,5- penta
The solution system of diamine salts is the mixture of the inorganic salts containing 1,5- pentanediamines or aqueous solutions of organic salts
System, can be pure solution system, can also include microorganism or compound impurities of solid etc., will not
Extracting method on the present invention produces influence.
Specifically, the solution system of the present invention for containing 1,5- pentanediamine salt refers to lysine salt
Solution reacts obtained pentanediamine salting liquid in the presence of lysine decarboxylase (LDC);Or
The pentanediamine salting liquid that direct fermentation is obtained.The present invention is to pentanediamine salt enzymatic conversion liquid or direct fermentation
The specific preparation method for preparing pentanediamine is not particularly limited, and those of ordinary skill in the art can root
Determine to select specific raw material according to prior art, it is determined that the technological parameter of specific enzymatic conversion process,
So as to obtain the solution system of the salt of pentanediamine containing 1,5-.
Wherein, the lysine salt that pentanediamine is produced for enzymatic conversion can be the inorganic of lysine
Salt or organic salt, lysine hydrochloride such as on the market, lysine sulphate commodity are molten
The lysine salt solution generated in Xie Shui.And for example biofermentation production lysine hydrochloride, rely
Propylhomoserin sulphate finished product or zymotic fluid, are dissolved in water the lysine salt solution of generation.Industrial big
During scale fermentation production lysine, culture medium uses ammonium sulfate as one of nitrogen source, therefore sends out
Contain substantial amounts of sulfate radical in zymotic fluid, zymotic fluid can also be used as lysine salt solution.Lysine
Zymotic fluid can directly use fermenation raw liquid, and what can also be obtained its further removal of impurities is pretreated
Zymotic fluid, such as removes the fermentation obtained after thalline by centrifugation, filtering or membrane filtration processing
Clear liquid, or lysine fermentation liquor is added such as activated carbon decolorizing, it is filtrated to get the lysine salt through decolouring
Solution.
Above-mentioned lysine decarboxylase refers to that can act on lysine or salt generates the enzyme of 1,5- pentanediamines.
Lysine decarboxylase can be the zymotic fluid of lysine decarboxylase, or by centrifuging or filtering or other
The decarboxylase cell that technological means is obtained, or broken cell, or zymotic fluid are filtered out and obtained after cell
Zymotic fluid clear liquid, or refined enzyme.It can also be the mixture of two or more enzymes.Produce lysine
The microorganism of decarboxylase can be wild strain or mutagenic strain or pass through base
Because of the bacterial strain of restructuring.
The present invention has no particular limits to the technique of lysine decarboxylic reaction, can use existing any
Enzymatic conversion technology, or by those of ordinary skill in the art make simple improvement in prior art.
For example, Zhu Jing (" microorganism conversion 1B is the research of cadaverine ", Master's thesis,
University Of Science and Technology Of Tianjin, in March, 2009) propose following four method:
(1), directly react:Lysine hydrochloride is directly appended in lysine decarboxylase zymotic fluid
To being 0.05mol/kg to concentration of substrate, 2h, molar yield 36.05% are reacted.
(2), buffer system enzyme reaction:Changed with 0.6N acetate buffer buffering reaction systems pH,
Final concentration of 0.22mol/kg of the lysine hydrochloride in cushioning liquid, reacts 2h, mole conversion
Rate 81.30%.
(3) pH enzyme reactions, are controlled:Lysine hydrochloric acid in strong acid control reaction pH5-6, enzyme reaction system
Salinity 0.22mol/kg, reacts 2h, molar yield 94.97%.
(4) pH enzyme reactions in batches, are controlled:Initially rely ammonia in strong acid control reaction pH5-6, reaction system
Acid hydrochloride concentration 0.22mol/kg, reaction certain time separation product constantly in situ and enzyme, turn eventually
Change substrate 0.87mol/kg, cadaverine yield is 94.61%.
And for example, Chinese patent CN 102782146A are disclosed before enzymatic conversion to expression lysine decarboxylation
The microorganism of enzyme carries out the modes such as freeze-thaw, heat treatment, lysine salt and handled, to improve efficiency.
Japanese documentation JP 20050147171 discloses using the lysine carbonate aqueous solution as substrate
Enzymatic is carried out, and pH is adjusted with carbon dioxide.
And for example, Application No. ZL 201410004636.3 Chinese patent is disclosed is sent out with lysine
Zymotic fluid carries out decarboxylic reaction and prepares 1,5- pentanediamines.
In lysine decarboxylic reaction, other compositions can be additionally added as needed, such as inorganic salts,
Vitamin or other contribute to any additive of enzyme reaction process.
In lysine decarboxylic reaction, reaction temperature is typically more than 20 DEG C, less than 60 DEG C.
Pentanediamine salt zymotic fluid of the present invention refers to by gene technology, can generate bad ammonia
The expression of lysine decarboxylase is raised in the bacterial strain of acid, or recombination expression lysine decarboxylase can be
The lysine of generation is synchronously converted into pentanediamine in fermentation process, thus directly obtain containing pentanediamine
The zymotic fluid of salt.The present invention is not required particularly recombinant bacterium, as long as pentanediamine can be obtained.
For example, " One-step production 1, the structure of 5- pentanediamine Corynebacterium glutamicum gene engineering bacterias " (ox
Great waves etc., Chinese biological engineering magazine, 2010,30 (8):One plant 93-99) is disclosed with honeycomb
Hough Buddhist nun bacterium (Hafniaalvei) genome is template, is expanded by PCR, obtains lysine and takes off
Decarboxylase gene ldc, and with Escherichia coli (Escherichia coli)/Corynebacterium glutamicum
(Corynebacteriumglutamicum) shuttle plasmid is carrier, the purpose base that amplification is obtained
Because fragment is cloned into Corynebacterium glutamicum, the recombinant bacterial strain of acquisition.And for example, PCT/CN
2015/094121 discloses the method that fermentation method directly produces 1,5- pentanediamines.Those skilled in the art
It should know how to be joined according to the component, ratio and zymotechnique of specific recombinant bacterium Optimal Medium
Number.Pentanediamine salt zymotic fluid can be that the fermenation raw liquid or fermenation raw liquid directly obtained is removed
Treatment fluid after miscellaneous, includes but is not limited to, and removes thalline, the zymotic fluid gone after depigmentation etc., this
Outside, pentanediamine salt zymotic fluid can also be the concentrate after fermenation raw liquid or treatment fluid concentration.Specifically
Removal of impurities, concentration method can use any applicable prior art.
In the method that the present invention is provided, it is firstly added alkaline matter and is dissociated with pentanediamine reactant salt
1, the 5- pentanediamines and inorganic salts of state, then contain free state 1,5- pentanediamines and nothing by gained
The solution system of machine salt carries out distilling/steaming in vacuum scraper drying device, under given conditions
Hair, obtains the aqueous solution containing pentanediamine, so as to reach the purpose for extracting pentanediamine.
In the present invention, the step of described " distillation/evaporation ", refers to containing free state 1,5- penta 2
The solution system of amine is heated, and evaporates water therein and the relatively low pentanediamine of boiling point, then will
The water vapour containing pentanediamine obtained by evaporation is collected, so as to obtain the water-soluble of 1,5- pentanediamines
Liquid, the operating procedure is that those skilled in the art know or are readily available.
In an embodiment of the method according to the invention, the vacuum of distillation/evaporation can be
- 0.12~-0.05MPa, specifically, the vacuum of distillation/evaporation can be -0.05MPa, -0.06
MPa、-0.07MPa、-0.08MPa、-0.09MPa、-0.10MPa、-0.11Mpa;Enter one
Step ground, vacuum preferably can be 0.07~0.01MPa, more preferably can be -0.095~-0.09MPa.
The pressure value is gauge pressure value.
In an embodiment of the method according to the invention, the temperature of distillation/evaporation can be
125~250 DEG C, specifically, the temperature of distillation/evaporation can for 125 DEG C, 130 DEG C, 135 DEG C, 140
℃、145℃、150℃、155℃、160℃、165℃、170℃、175℃、180℃、185℃、
190℃、195℃、200℃、205℃、210℃、215℃、220℃、225℃、230℃、235
℃、240℃、245℃、250℃.It can be further preferably 150~230 DEG C, more preferably can be
170~210 DEG C, most preferably can be 190~200 DEG C.In one preferred embodiment, can be using slow
Slowly the mode heated up.
As it was previously stated, the solution system available sources of the pentanediamine salt Han 1,5- are more in the prior art, this hair
Bright method is applied to all 1,5- pentanediamine salt species, including but not limited to common sulfate, carbon
Hydrochlorate, phosphate, hydrochloride, dicarboxylate etc..Dicarboxylate therein can be 1,5- pentanediamines
With salt of the carbon number for 2-12 dicarboxylic acids formation, the adipate of including but not limited to 1,5- pentanediamines
Deng.In general, concentration range of 1, the 5- pentanediamines salt in solution system can be 5wt%~35wt%,
Preferably 20wt%~30wt%.
In an embodiment of the method according to the invention, in the solution system of the pentanediamine salt containing 1,5-
One or more in sulfate, carbonate and phosphate comprising 1,5- pentanediamines.When 1,5- pentanediamines
Salt be sulfate, carbonate and it is phosphatic one or more when, according to conventional method using sodium hydroxide,
The strong base substances such as potassium hydroxide are reacted, and the inorganic salts due to generation in subsequent evaporation processing procedure hold
Easily separate out, so as to cause pentanediamine yield relatively low, but these will not be produced when using the method for the present invention
Phenomenon, can still obtain preferable pentanediamine yield, therefore the method for the present invention is particularly suitable for use in foregoing feelings
Shape.
In one preferred embodiment, 1, the 5- penta included in the solution system of the pentanediamine salt containing 1,5-
Sulfate, carbonate and the phosphatic mole of diamines are not less than 1,5- pentanediamines in the solution system
The 70% of salt integral molar quantity, preferably not lower than 75%, more preferably it is not less than 80%, further preferably
To be not less than 85%, most desirably not less than 90%.Included in the solution system of the salt of pentanediamine containing 1,5- a large amount of
During the salt of mentioned kind, method of the invention can also obtain higher pentanediamine yield.Percentage herein
Than representing to work as when the sulfate containing single 1,5- pentanediamines, carbonate and phosphate, single 1,5- penta 2
Sulfate, carbonate and the phosphate of amine account for the percentage of 1,5- pentanediamines salt integral molar quantity in solution system;
Or represent, when containing the sulfate of 1,5- pentanediamines, carbonate and at phosphatic two or three,
Sulfate, carbonate and the phosphatic summation of both or three kinds of 1,5- pentanediamines account for solution body described in 1
The percentage of 1,5- pentanediamines salt integral molar quantity in system.
In the method that the present invention is provided, applicable alkaline matter can be common inorganic base, can include
Sodium hydroxide, potassium hydroxide of strong basicity etc., can also include the calcium hydroxide of slightly solubility, magnesium hydroxide,
Calcium oxide, magnesia etc., in an embodiment of the method according to the invention, it is adaptable to the present invention
Alkaline matter include but is not limited to sodium hydroxide, potassium hydroxide, ammoniacal liquor, calcium hydroxide, magnesium hydroxide,
Calcium oxide, magnesia etc..
In the understanding of prior art, alkaline matter usually using sodium hydroxide, potassium hydroxide of strong basicity etc.,
And when using weak base or slightly solubility alkali when, it is generally recognized that due to pentanediamine alkalescence it is stronger, addition weak base or
Slightly solubility alkali is difficult to make pentanediamine reactant salt completely, the solid base and the slightly solubility of generation remained in system
The solid impurities such as inorganic salts precipitation can influence the yield of pentanediamine.It was found by the inventors of the present invention that for penta
The types such as sulfate, phosphate, the carbonate of diamines, it is different from prior art idea, add slightly solubility
Alkali such as calcium oxide, calcium hydroxide, magnesium hydroxide etc., make it generate the inorganic of slightly solubility in solution system
Salt is precipitated, and the generation of precipitation has promoted the continued dissolution process of above-mentioned slightly solubility alkali in the solution, so as to
Pentanediamine salt constantly, is stably converted to pentanediamine, substantially increase the conversion ratio of pentanediamine, and
And slightly solubility alkali can also substantially reduce manufacturing cost.Based on this, in a reality of the method according to the invention
Apply in mode, when sulfate, carbonic acid that 1,5- pentanediamines are included in the solution system of the pentanediamine salt containing 1,5-
During one or more in salt, phosphate, alkaline matter accordingly includes calcium hydroxide, magnesium hydroxide, oxygen
Change calcium, the one or more of magnesia to react.
There is relation in the source of the alkaline matter used in the present invention, its purity and raw material, as long as impurity
In without having an impact the composition of pentanediamine product quality, be used equally for the present invention.In some embodiments
In, other materials not with pentanediamine reactant salt can be included in alkaline matter.For example in calcium oxide
Carbonic acid calcium impurities, calcium carbonate is present in industrial oxidation as the impurity in calcium oxide production process
In calcium product, but it does not influence the reaction in the present invention.
In the present invention, the addition manner of alkaline matter is not particularly limited, and can once put into,
Can also put into batches, can also be and put into each component of alkaline matter mixture respectively, or
It is once to be added after first mixture mixing is finished.Preferably, sodium hydroxide, potassium hydroxide etc. are strong
Alkaline matter can be added by 10~50% aqueous solution form of mass percent concentration.Alkali during input
Property material can use single kind, can also use two kinds or more of mixture.
In general, it can be determined to add adding for alkaline matter according to the amount of 1,5- pentanediamines salt in solution
Dosage.Alkaline matter can be well over required theoretical amount, to ensure that reaction is complete.In basis
In one embodiment of the method for the present invention, the consumption of alkaline matter is:It can make to contain 1,5- penta
Pentanediamine in the solution system of diamine salts forms 1~1.5 times of the minimum amount of free state completely, excellent
Elect 1~1.2 times, more preferably 1~1.1 times as.In one preferred embodiment, monovalence sun from
The mol ratio of sub- alkaline matter (such as sodium hydroxide, potassium hydroxide) and 1,5- pentanediamine salt can be with
For (2~3):1, be preferably (2~2.4):1, more preferably (2~2.2):1;Divalence sun from
Sub- alkaline matter (such as calcium hydroxide, magnesium hydroxide, calcium oxide) is rubbed with 1,5- pentanediamine salt
You are than being (1~1.5):1, be preferably (1~1.2):1, more preferably (1~1.1):1.
In an embodiment of the method according to the invention, in step S1, the alkalescence is added
Temperature during material can be 20~90 DEG C, preferably 20~65 DEG C, more preferably 25~45 DEG C, enter
One step is preferably 30~40 DEG C.In certain embodiments, pentanediamine salt and alkali substance reaction time are big
In 1 hour, preferably greater than 1.5 hours.
In the present invention, after the pentanediamine in the pentanediamine aqueous solution that distillation/evaporation is obtained can be separated from water
Obtain qualified pentanediamine product.Resulting 1, the 5- pentanediamine aqueous solution, can be further by normal
The aqueous solution processing mode of rule obtains pentanediamine sterling, and including but not limited to rectifying etc. can also be straight
Connect and participate in downstream reaction such as polymerisation etc. as raw material.In some preferred embodiments of the invention,
Also first the solution system obtained by step S1 can be concentrated before distillation/evaporation.Due to the boiling of water
Point is than the low boiling point of pentanediamine, and the purpose of concentration is heated using the heating medium compared with low-energy-efficiency
Concentration, to reach the purpose of energy-conservation, and can improve the dense of pentanediamine product obtained by distillation/evaporation stage
Degree.Mode and cycles of concentration to concentration can be carried out according to actual needs, without special in the present invention
Limitation.
In an embodiment of the method according to the invention, before step S1 also include it is degerming and
/ or decolourize pre-treatment step.Degerming, decolorization can be using the common technology in this area.
In an embodiment of the method according to the invention, the rotating speed of vacuum scraper drying device
It can be 0.05~15rpm, preferably can be 0.1~10rpm, more preferably can be 0.2~5rpm,
Further preferably can be 0.5~1rpm.
In an embodiment of the method according to the invention, the charging rate of vacuum scraper drying device
Can be 5~50kg/m2/ h, preferably can be 10~40kg/m2/ h, more preferably can be 18~30
kg/m2/h。
In the embodiment of the method according to the invention, vacuum scraper drying device scrapes film thickness
It can be 0.4~2mm, preferably can be 0.5~1.5mm, more preferably can be 0.8~1mm.
In an embodiment of the method according to the invention, vacuum scraper drying device can be single rolling
Cartridge type, or double drum type.
In an embodiment of the method according to the invention, vacuum scraper drying device includes true
Empty device, the rotary drum body being arranged among vacuum plant, feed liquid disk, scraper, and it is arranged at institute
The material residue collection device below scraper is stated, rotary drum body is driven by rotary shaft and rotated;Positioned at feed liquid
The solution system obtained by step S1 in disk forms thin layer on rotary drum body, through S2 steps, then
Material residue is scraped by the scraper, and collects and discharges through the material residue collection device.
As shown in Figure 1, 2, 3, by taking single tumbling as an example, vacuum scraper drying device of the invention includes:
Vacuum plant 5, rotary drum body 1, rotary shaft 2, feed liquid disk 3, scraper 4, and material residue collection device
7, wherein, rotary drum body 1, rotary shaft 2, feed liquid disk 3 and scraper 4 are arranged in vacuum plant 5,
Material residue collection device 7 is arranged at the lower section of scraper 4, and the material residue for collecting discharge, rotary drum body 1 is wrapped
Coaxial inner cylinder 101 and outer barrel 102 is included, wherein containing the heating medium for heating, vacuum plant 5
On be provided with gas vent 501 for discharging gas, gas vent 501 connects through a condensing unit
Pentanediamine collection device is connected to, for condensing and collecting in vacuum scraper drying device what is evaporated/distill out
Pentanediamine water vapour.Vacuum scraper drying device also include power set 6 (including motor, reductor,
Gear etc.).When the vacuum scraper drying device is run, feed liquid to be evaporated (i.e. the inventive method step
The solution system of 1, the 5- pentanediamines containing free state obtained by S1) it is placed in feed liquid disk 3, power set
6 driving rotary shafts 2 drive rotary drum body 1 to rotate, and feed liquid and the barrel of outer barrel 102 of rotary drum body 1 connect
Touch, adhere on the barrel of deep sorrow 102 of rotary drum body 1, while feed liquid is through leading in deflector 103
Stream heating medium heating, the relatively low pentanediamine of boiling point and water vapour are evaporated and by the row of gas vent 501
Go out vacuum scraper drying device, then after the condensation of external condenser, received in pentanediamine collection device
Collection, rotary drum body 1 is constantly rotated, and the material residue after pervaporation/evaporation is scraped by scraper 4, falls into material residue
Collection device 7 is simultaneously collected by it and discharged.
In an embodiment of the method according to the invention, as shown in Fig. 2 material residue collects dress
Putting 7 mainly includes material residue funnel 701 and material residue collection bucket 702, and material residue funnel 701 is located at scraper
4 lower section, for collecting the material residue that scraper 4 is scraped, material residue passes through material residue passage 703, falls into material
In slag collection bucket 702, and collect wherein and discharge in good time.It is provided with material residue collection bucket 702
The inlet valve 704 and outlet valve 705 of entrance and the discharge of material residue are controlled, in addition, material residue is received
Vacuum breaker 706 and pressure-regulating valve 707 are additionally provided with collection bucket 702.Vacuum scraper is dried
During plant running, the domestic demand of vacuum plant 5 maintains certain vacuum, during without disposing material residue, enters
Mouth valve 704 is in opening state, and material residue collection bucket 702 collects material residue.When material residue collection bucket 702
In material residue when needing discharge, close inlet valve 704, and open pressure-regulating valve 707, make air
Enter in material residue collection bucket 702, after wherein air pressure recovers normal pressure, open the row of outlet valve 705
Material residue is unloaded, after material residue discharge, outlet valve 705 is closed, vacuumized while opening vacuum breaker 706,
Make the air pressure in material residue collection bucket 702 gradually same or like with air pressure in material residue passage 703, this
When open inlet valve 704, continue to collect material residue, and continuous firing shape be always maintained in vacuum plant 5
State, material residue funnel 701 also can uninterruptedly collect material residue.Pass through the tune of two regulating valves 706,707
Section, coordinates other structures, it is possible to achieve vacuum scraper drying device runs without interruption.
In an embodiment of the method according to the invention, the He of inner cylinder 101 of rotary drum body 1
The deflector 103 for diversion heating medium is provided between outer barrel 102.In a preferred implementation
In mode, deflector is distributed in the shape of a spiral.It is generally used for the heating medium of vacuum scraper drying device
For conduction oil, it flows between the inner cylinder 101 and outer barrel 102 of rotary drum body 1 plays heating work
With, the heating effect of vacuum scraper drying device is directly determined, deflector 103 is set wherein, can
Guiding heating medium, especially heating oil more uniformly flow between inner cylinder 101 and outer barrel 102
It is dynamic, so as to play more uniform, stable heating effect, it can also reduce heating cost.
In an embodiment of the method according to the invention, as shown in Figure 1,3, vacuum plant
Agitating device 8 is additionally provided with 5, the feed liquid for stirring to be distilled/evaporation in feed liquid disk 3, stirring
Device includes agitator 801, stirrer gear drum 802 and stirring gear 803;801, agitator
In the top of feed liquid disk 3 and the bottom of feed liquid disk 3 is preferably parallel to, for the stirring of feed liquid, stirred
It can be any type of agitator to mix device 801, such as can be blade-carrying agitating paddle;
Stirring gear 803 is connected by stirrer gear drum 802 with agitator 801, and stirring gear 803 is with turning
Moving axis 2 is connected, and the driving rotary shaft 2 of power set 6 drives agitator 801 to run, and is stirred as driven
Mix oar rotation.
In an embodiment of the method according to the invention, the draw ratio of rotary drum body 1 can be with
It preferably can be 0.8~2 for 0.6~2.6, more preferably can be 1.0~1.5.
In an embodiment of the method according to the invention, the length of rotary drum body 1 can be
1.5~5m, preferably can be 2~2.5m.
In an embodiment of the method according to the invention, scraper 4 can be copper coin scraper,
Using multistage blade reduplicative formses, slitless connection between adjacent knife blades;Scraper 4 is set by frame
In on rotary drum body 1.
Below by embodiment, the present invention is described in detail, so that the features and advantages of the present invention
Become apparent from.It should be understood that the present invention is not limited only to embodiment listed herein.
Such as it is not specifically stated, embodiment and all pressure of comparative example are gauge pressure.
The purity of pentanediamine or its salt is that gas-chromatography normalization method is measured.The detection method of pentanediamine is used
Nuclear magnetic resonance instrument detects the characteristic absorption peak of pentanediamine.
The pentanediamine concentration mentioned in following examples each means the mass concentration in terms of pentanediamine.
Embodiment 1
Take 1,5- pentanediamine salt enzymatic conversions liquid (wherein, the quality percentage of 1,5- pentanediamines salt of carrier
Specific concentration is 35%, the sulphates content 70% of 1,5- pentanediamine, phosphatic content 10%, percentage
Than to account for the molar percentage of 1,5- pentanediamine salt), lime powder (purity more than 90%) is added,
The mol ratio of calcium oxide and 1,5- pentanediamine salt is 1.1:1, stir 2h at a temperature of 40 DEG C;So
Rear feeding is into the vacuum scraper drying device of the present invention, charging rate 20kg/m2/ h, vacuum scraper
The rotating speed 0.8rpm of drying device, scrapes film thickness 1mm, 200 DEG C of heat conduction oil temperature;
In vacuum scraper drying device, the solution system of foregoing gained is evaporated, the evaporation exists
Carried out under the conditions of vacuum -0.09~-0.095MPa, 190 DEG C of temperature.
The yield 99.2% of pentanediamine.
Embodiment 2
Take 1,5- pentanediamine sulfate enzymatic conversion liquid (wherein, the quality of 1,5- pentanediamines salt of carrier
Percent concentration is 30%), to add calcium oxide, and the mol ratio of calcium oxide and 1,5- pentanediamine salt is
1.2:1, stir 1.5h at a temperature of 40 DEG C;Then feed to the vacuum scraper of the present invention and dry dress
In putting, charging rate 18kg/m2/ h, rotating speed 2rpm, scrape film thickness 0.8mm, heat conduction oil temperature
200℃;
In vacuum scraper drying device, the solution system of foregoing gained is evaporated, the evaporation exists
Carried out under the conditions of vacuum -0.08MPa, 190 DEG C of temperature.
The yield 98.9% of pentanediamine.
Embodiment 3
1, the 5- pentanediamine salt enzymatic conversion liquid of carrier is taken, its pentanediamine mass percent concentration is determined
For 20%.Evaporated on pressure -0.095MPa Rotary Evaporators, control 90 DEG C of bath temperature, it is dense
The mass percent concentration for being reduced to 1,5- pentanediamine salt is 15%, adds calcium hydroxide, calcium hydroxide
1.05:1, stir 1.5h at a temperature of 25 DEG C;Then feed to the vacuum scraper of the present invention and dry dress
In putting, charging rate 15kg/m2/ h, rotating speed 1rpm, scrape film thickness 0.6mm, heat conduction oil temperature
180℃;
In vacuum scraper drying device, the solution system of foregoing gained is evaporated, the evaporation exists
Carried out under the conditions of vacuum -0.08MPa, 170 DEG C of temperature.
The yield 97.5% of pentanediamine.
Embodiment 4
Take pentanediamine salt enzymatic conversion liquid (wherein, the mass percent concentration of 1,5- pentanediamines salt be 10%,
Sulfate radical accounts for the 89% of anion total mole number, and carbonate accounts for the 10% of anion total mole number, chlorine
Ion account for anion total mole number 1%), add sodium hydroxide, sodium hydroxide and 1,5- pentanediamine
The mol ratio of salt is 2.2:1, stir 1.5h at a temperature of 25 DEG C;Then feed to the present invention it is true
In empty scraper plate drying device, charging rate 15kg/m2/ h, rotating speed 3.5rpm, scrape film thickness 0.5mm,
180 DEG C of heat conduction oil temperature;
In vacuum scraper drying device, the solution system of foregoing gained is evaporated, the evaporation exists
Carried out under the conditions of vacuum 0.065MPa, 150 DEG C of temperature.
The yield 96.5% of pentanediamine.
Embodiment 5
Take concentrate (wherein, 1, the 5- pentanediamines salt of 1, the 5- pentanediamine salt enzymatic conversion liquid of carrier
Mass percent concentration is 18.5%, sulfate, carbonate and the phosphatic total amount of 1,5- pentanediamine
The 95% of 1,5- pentanediamine salt integral molar quantities is accounted for, remaining is the hydrochloride of 1,5- pentanediamines), add hydrogen
The mol ratio of magnesia, magnesium hydroxide and 1,5- pentanediamine salt is 1.5:1, stirred at a temperature of 65 DEG C
Mix 1h;Then feed into the vacuum scraper drying device of the present invention, charging rate 10kg/m2/ h,
Rotating speed 0.5rpm, scrapes film thickness 0.8mm, 200 DEG C of heat conduction oil temperature;
In vacuum scraper drying device, the solution system of foregoing gained is evaporated, the evaporation exists
Carried out under the conditions of vacuum -0.08MPa, 150 DEG C of temperature.
The yield 95.8% of pentanediamine.
Embodiment 6
Take pentanediamine salt enzymatic conversion liquid (wherein, the mass percent concentration of 1,5- pentanediamines salt be 13%,
Sulfate radical accounts for the 75% of anion total mole number, and phosphate radical accounts for the 10% of anion total mole number, carbon
Acid group accounts for the 10% of anion total mole number, chlorion account for anion total mole number 5%), add
The mol ratio of sodium hydroxide, sodium hydroxide and 1,5- pentanediamine salt is 2.1:1, at a temperature of 35 DEG C
Stir 1.2h;Then feed into the vacuum scraper drying device of the present invention;Charging rate
20kg/m2/ h, the rotating speed 0.8rpm of vacuum scraper drying device, scrapes film thickness 1.0mm, conduction oil
200 DEG C of temperature;
In vacuum scraper drying device, the solution system of foregoing gained is evaporated, the evaporation exists
Carried out under the conditions of vacuum -0.085MPa, 160 DEG C of temperature.
The yield 94% of pentanediamine.
Embodiment 7
Taking pentanediamine salt enzymatic conversion liquid, (wherein, the mass percent concentration of 1,5- pentanediamines salt is
18%) mol ratio of, addition potassium hydroxide, potassium hydroxide and 1,5- pentanediamine salt is 2:1,
1.2h is stirred at a temperature of 35 DEG C;Then feed into the vacuum scraper drying device of the present invention;Charging
Speed 25kg/m2/ h, the rotating speed 1.0rpm of vacuum scraper drying device, scrapes film thickness 1.5mm, leads
220 DEG C of hot oil temperature;
In vacuum scraper drying device, the solution system of foregoing gained is evaporated, the evaporation exists
Carried out under the conditions of vacuum -0.075MPa, 175 DEG C of temperature.
The yield 94.8% of pentanediamine.
Comparative example 1
The pentanediamine sulfate enzymatic conversion liquid of 600g carriers, determines pentanediamine mass concentration 15.1%.
76g sodium hydroxide powders (chemistry is pure) are slowly added to while stirring, control temperature below 60 DEG C,
Stirring 120 minutes.100g beades are added into mixed solution and strengthen stirring, in pressure
Evaporated on -0.095MPa Rotary Evaporators, step up the temperature of oil bath heating to 180 DEG C, obtain
The aqueous solution of the 515g containing pentanediamine 11.3%.The yield 64.2% of pentanediamine, eggplant type bottom of bottle precipitate
Sticky, poor fluidity, pressure, which is put to normal pressure, voluntarily to be poured out, bottom of bottle residue knot during room temperature
Wall caking phenomenon is serious.
Comparative example 2
1, the 5- pentanediamine sulfate enzymatic conversion liquid of 100kg carriers, determines 1,5- pentanediamine concentration
15.1%.25kg sodium hydroxide solutions (mass concentration 50%) are added, temperature are controlled at 30 degree,
Stirring 180 minutes, mixed solution is steamed in pressure -0.095MPa in vertical evaporating kettle heating stirring
Hair, steps up the temperature of oil bath heating, is gradually increased to 200 DEG C from 70 DEG C, moisture evaporation with
Afterwards, inorganic salts are gradually separated out, and kettle base solution is sticky, and stirring is difficult, finally give 62.1kg containing 1,5-
The aqueous solution of pentanediamine 16.7%.The yield 48.7% of 1,5- pentanediamines.
The method 1 provided from embodiment and comparative example, the present invention, the high income of 5- pentanediamines, and
Intractable evaporation discarded object will not be produced, production efficiency, reduction production cost can be increased substantially.And
And, can be without filtering before solution system evaporation, target product yield is unaffected, further simplify
Technological process, reduce cost.
Although in order to illustrate the present invention, having been disclosed for the preferred embodiments of the invention, this area
It will be appreciated by the skilled person that not departing from the feelings of present inventive concept that claims are limited and scope
Under condition, various modifications, addition can be made to the present invention and is replaced.