CN110143899A - A kind of production method and device of the methionine complexing metal salt of clean and environmental protection - Google Patents
A kind of production method and device of the methionine complexing metal salt of clean and environmental protection Download PDFInfo
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- CN110143899A CN110143899A CN201910504896.XA CN201910504896A CN110143899A CN 110143899 A CN110143899 A CN 110143899A CN 201910504896 A CN201910504896 A CN 201910504896A CN 110143899 A CN110143899 A CN 110143899A
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- C07—ORGANIC CHEMISTRY
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- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
The present invention relates to the preparation methods and device of a kind of methionine complexing metal salt of clean and environmental protection, the following steps are included: (1) is proportionally added into methionine, water and trace elements metal salt in synthesizer, heating is completely dissolved, it is warming up to 80 DEG C~105 DEG C, heat preservation 0.5 hour to 2.0 hours, obtains methionine complexing metal saline solution；(2) the methionine complexing metal saline solution convection drying for obtaining step (1) obtains methionine complexing metal product salt after dry to constant weight.The present invention is generated with no three wastes, and complexing of metal ion rate is high, and the product of production avoids a large amount of dust pollution without pulverizing and sieving；PH is adjusted without using any alkali during complex reaction, there is the features such as easy to operate, high income, production cost is low, and the methionine complex salt suitable for various trace elements metal salt produces.
Description
Technical field
The invention belongs to the complex compound preparation field that organises, the methionine complexing metal salt of especially a kind of clean and environmental protection
Production method and device.
Background technique
Microelement is highly important nutritive additive, the micro member that tradition generally uses in feed, premix
Plain additive is mainly the inorganic salts such as sulfate, chlorate, oxide, they have many defects, such as: in Animal nutrition due to
It chemically reacts complicated in digestion process, vulnerable to the influence of the ingredients such as phosphate, phytic acid in feed, and forms infusible precipitate,
Biological value is reduced, affects and is absorbed and utilized；Various trace element ions, there are antagonism, influence to inhale in absorption process
It receives and utilizes；Inorganic salts generally have the crystallization water, easy moisture absorption agglomeration in feed processing；Inorganic salts destroy vitamin and grease etc.
It acts on stronger；Some feed factories use high manganese high zinc diets, produce effects not high, and serious pollution environment etc..
Methionine also known as methionine are one of the essential amino acids for constituting animal body, are a kind of antioxidant, can be effectively
Remove the intracorporal free radical of biology.Methionine is uniquely containing the amino acid of sulphur in essential amino acid, it participates in first in animal body
The synthesis of the transfer of base and the metabolism of phosphorus and adrenaline, choline and creatine；It is the raw material of synthetic proteins matter and cystine；In first
Under normal circumstances, methionine is after animal body absorbs, under the action of various aminoacidases, mainly in liver, kidney to base donor
It is decomposed in dirty, anabolism, be transformed into protein, nitrogenous active material or be converted to energy for body growth development
Amount, therefore can be used for preventing and treating the liver diseases such as chronic or acute hepatitis, cirrhosis, it can also be used to alleviate arsenic, chloroform, tetrachloro
Change the toxic reaction of the harmful substances such as carbon, benzene, pyridine, quinoline and heavy metal.
With the methionine complexing metal salt of the metal salt coordination of methionine and copper, manganese, cobalt, nickel, chromium (trivalent), both it was used for
Microelement-supplementing is also used to assist in the treatment of some diseases, if chromium methionine is in food and medicine industry, is mainly used for auxiliary and controls
II patients with type Ⅰ DM is treated, the auxiliary element of slimming health food, therefore a kind of its nutritional supplementation as ideal health are also served as
Agent and treatment adjuvant, are widely used in feed, food and pharmaceuticals industry, and certain research has been obtained.
Chinese patent CN101914048A discloses a kind of preparation method of cobalt methionine, comprising the following steps: (1) at
Reactant salt step: by methionine, basic cobaltous carbonate, initiator, water investment reaction kettle, stirring is heated 70-80 DEG C of reaction, is made
Carbon dioxide overflows, and generates cobalt methionine；(2) baking step: isolated granular product is placed in ventilative above and below
In dry sieve, drying, obtained product sieving obtains cobalt methionine product.This preparation method in process of production, uses alkali formula
Cobalt carbonate and initiator, guarantee obtain granular product, are conducive to drying, do not have to crush, avoid dust, have and realize simple, behaviour
Make convenient feature, has saved the investment of production equipment, improved production efficiency.
Chinese patent CN106674068A discloses a kind of preparation method of manganese methionine, this method include salt-forming reaction and
It dries two steps, the specific steps are as follows: salt-forming reaction: methionine, basic carbonate manganese, benzoic acid and water is put into reaction kettle
In, it is stirred, reaction is heated at 65 DEG C, overflows carbon dioxide, generate manganese methionine, the methionine, basic carbonate
The mass ratio of manganese, benzoic acid and water is 7:2:3:30；Drying: isolated granular product is placed in ventilative above and below
It in stainless steel dry sieve, is put into drying box and dries, to get manganese methionine product is arrived, the drying is warm for obtained product sieving
Degree is 110 DEG C.The present invention has the advantages that the present invention is in process of production, using basic carbonate manganese and initiator, guarantee to obtain
Granular product is conducive to drying, does not have to crush, avoids the generation of dust, have and realize simple, easy to operate feature, saves
The investment of production equipment, improves production efficiency.
Chinese patent CN101914047A discloses a kind of preparation method of manganese methionine, comprising the following steps: (1) at
Reactant salt step: by methionine, basic carbonate manganese, initiator, water investment reaction kettle, stirring, 70 DEG C of -80 DEG C of heating are reacted,
Carbon dioxide is overflowed, manganese methionine is generated；(2) baking step: isolated granular product is placed in upper and lower ventilative
Stainless steel dry sieve in, be put into drying box and dry, the sieving of obtained product is to get to manganese methionine product.This preparation side
The granular product that method obtains, is easily dried, and reduces protection and equipment, has saved equipment investment, reduced operating cost.
Chinese patent CN107337625A discloses a kind of preparation method of feed grade hydroxy methionine manganic chelates, including
Following steps: metering sodium hydroxide reagent A, is added into the inorganic salt solution of manganese, obtains solid formation；B, washing solid formation with
Remove wherein soluble component；C, add water homogenate into washing slag；D, according to mole of manganese content in slurry and hydroxy methionine
Ratio≤0 .5 ratio is added hydroxy methionine and carries out chelatropic reaction；E, reaction product obtains product by post-processing.This hair
Bright advantage is: 1) the higher hydroxy methionine manganic chelates product of purity can be prepared, it is preferably to be used as feed addictive
It uses；2) chelatropic reaction rate is fast, and low energy consumption, at normal temperature can faster rate carry out, production method is easy, is conducive to
It is promoted in industry.
Chinese patent CN101704774B discloses a kind of hydroxy methionine chelate of entitled hydroxyl nickel methionine,
Molecular formula is (C5H9O3S)2Ni, the hydroxyl nickel methionine are by the crystalline hydrate of nickel sulfate or nickel sulfate and hydroxyl egg ammonia
Aqueous acid, highly basic mixing obtain after being reacted.The hydroxyl nickel methionine can be used as animal feed additive and be applied, should
Application method is simple and convenient to operate, and all achieves obviously feeding effect after raising pig, poultry and ruminant.This is specially
The methionine hydroxy analog chelating nickel that benefit obtains is 2:1 type, and using sodium hydroxide, producing ammonium sulfate byproduct or sodium chloride are generated
A large amount of reluctant waste water.
Chinese patent CN102524541B discloses a kind of preparation method and applications of nickel methionine, including following step
It is rapid: to adjust pH value after inorganic nickel element compound and methionine are dissolved in water, then heat up；Or it is risen after methionine is dissolved in water
Inorganic nickel element compound is added after adjusting pH value in temperature；Or methionine mixed with lye after heat up, add inorganic nickel element
Compound；Reaction is most sufficiently stirred afterwards, is centrifuged, granulation is dried in the wet feed after centrifugation, finished product methionine after sieving
Nickel.
Chinese patent CN101914050A discloses a kind of preparation method of copper methionine, and this method is by methionine, alkali
Formula copper carbonate, initiator, water are passed through in reaction kettle, stirring, and 70 DEG C~80 DEG C heating reactions overflow its carbon dioxide.It generates
Copper methionine is then centrifuged for, dries, being sieved obtains copper methionine product.The inventive method in process of production, it is said that using alkali
Formula copper carbonate and its initiator, guarantee obtain granular product, are conducive to drying, do not have to crush, avoid the generation of dust, have real
Now simple, easy to operate feature, has saved the investment of production equipment, has improved production efficiency.What this method obtained is 2:1 type
Methionine chelate copper.
Chinese patent CN1995015B discloses a kind of side that feed grade methionine copper chelate is prepared using etching waste liquor
Method, belongs to the technical field that fine chemistry industry is intersected with environmental protection, it includes the following steps: to wiring board copper chloride etching waste liquid
It is refined, removes the objectionable impurities such as arsenic, lead；Water is added to be deployed into solution methionine raw material, concentration is 0.1~10%；It will
Methionine solution and purification waste cuprous chloride solution heating, temperature reach 20~100 DEG C；According to certain mol ratio, by methionine
Solution is mixed with any one or two kinds of waste cuprous chloride solutions；Molal quantity is added in the methionine should be not less than copper addition mole
Several 2 times；Acid adding or alkali in the solution that above-mentioned steps obtain, with adjust solution to pH value 4~8 reaction end；And
The temperature for keeping reaction system, reacts fully；Sediment is separated by solid-liquid separation；Sediment is washed with water；It is heavy by what is cleaned
Starch is dry, crushes, is sieved to get feed grade methionine copper chelate finished product.What this method obtained is 2:1 type methionine chelate
Copper.
The preparation method such as JP 6287173 of the chromium methionine chelate of reporting, PL 254171, in CN1218054A
It is provided, it requires to carry out in liquefied ammonia system mostly, these methods are synthesized using metallic sodium or lithium methide as substitute
Or the reaction condition of high temperature and pressure is needed, complex process does not have industrialized utilization value.It then develops in aqueous systems and makes again
The method of standby chromium methionine chelate.Preparation method in water system can be divided into following two:
(1) non-aqueous legal
Chinese patent CN 1523008A, CN 1329024C, United States Patent (USP) US 2007134300 and Teng Bing et al. (Teng Bing, Korea Spro
The preparation of friendly text chromium (III) chelate and relevant nature identify [J] Animal nutrition journal, 2000,12 (3): 19~
23) by D, after L- methionine and chromic salt are stirred sufficiently in water, under stiring with dense NaOH solution adjusting solution
PH makes the chromium methionine generated precipitate and be precipitated, and stands cooled and filtered, is sufficiently dried to obtain after filter cake water and ethanol washing
Chromium methionine product.
Chromium chloride is dissolved in after water by United States Patent (USP) US 20030228934 to be heated to boiling, and L- methionine is then added, stirs
Mixing dissolves solid, is cooled to 30 DEG C after continuing agitating and heating 30min, is then added dropwise sodium hydroxide solution thereto, solution by
Dirty-green becomes aubergine.Solution is evaporated to dryness by decompression, and solid removes sodium chloride with methanol extraction, then by methanol extraction liquid
It is evaporated to dryness, obtains chromium methionine product.
Above method operation is cumbersome, and precipitates product by the way that sodium hydroxide solution adjusting solution pH value is added dropwise
Method industrially without utility value, cannot achieve continuous production.
(2) hydration method
Zhang Hua et al. is using first adding chromium chloride to be hydrated 24 hours generation [Cr (H2O) 6] 3+, and by D, it is molten that L- methionine is dissolved in this
In liquid, come into full contact with reactant, then adjusting pH with 6mol/L NaOH solution precipitates the chromium methionine generated, then passes through
It cools down, be filtered, washed, being dried to obtain product (Zhang Hua, Wang Jing, Wang Qing, Xiang Wensheng.The conjunction of chromium-methionine chelate nutrition fortifier
At industrial [J].Food and fermentation industries, 2005,31 (4): 87~89).The method operating time is long, and is also to pass through
Sodium hydroxide solution adjusting pH, which is added dropwise, makes the method for product precipitating industrially without utility value, cannot achieve continuous production.
Patent CN102516142B discloses a kind of preparation method of chromium methionine chelate.This method is with D, L- egg ammonia
Sour, inorganic chromic salt is primary raw material, and using alcoholic solution as reaction medium, 30-90 DEG C of reaction temperature, the reaction time, 0.5-3 was small
When, chromium methionine chelate is prepared under normal pressure.
From the above, it can be seen that it is usually benefit that the egg base acid network (chela) of mainstream, which closes the production method of microelement metal, at present
It is raw material with methionine and inorganic microelement metal salt, adjusts pH value with sodium hydroxide or other alkali, however such method
It has the following problems: needing to adjust pH value using sodium hydroxide, consume a large amount of sodium hydroxide, a large amount of inorganic acid salt of by-product；
Production technology is complicated, and methionine network (chela), which closes several metal needs of microelement, will use organic solvent as release agent, organic solvent
High price and cumbersome waste water recycling device process, this be also cause methionine microelement network (chela) close price Ge Jugao
Not the main reason for not descending；When producing the methionine chelate metal ion of 2:1 type, need methionine excessive, this necessarily makes its egg
Contain methionine in the waste water of propylhomoserin loss and discharge；During the drying process, moisture evaporation is slow, easily agglomerates；Production to drying
Product pulverize and sieve processing, generate a large amount of dust, cause production environment poor, enterprise is difficult to mass production；Chromium has
Imitate that complexing rate is low, and bioavailability is low, unstable product quality, due to metal oxide and basic carbonate metal salt-stable compared with
Good, cannot dissociate metal ion out very well, and methionine network (chela), which closes in microelement metal, often contains inorganic metal salt, or
When adjusting pH using sodium hydroxide, cause to generate oxidized metal inclusions in the product, to influence the quality of product；Furthermore
Current methionine metal network (chela) reported in the literature is if close owner based on 2:1 type, and the seldom related document report of 1:1 type
Road.
In view of the above-mentioned deficiencies, by the production practices of inventor's many years, a kind of egg of novel clean and environmental protection is developed
The production method and device of propylhomoserin complexing metal salt.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of methionine complexings of novel clean and environmental protection
The production method and device of metal salt, this method can save equipment investment, avoid dust pollution, and operating procedure is simple, solve
Conventional production methods lead to the problem of a large amount of waste water and by-product inorganic salts, and to solve conventional production methods complexing rate low
The problem of.
The purpose of the present invention is in this way by realization:
A kind of production method and device of the methionine complexing metal salt of clean and environmental protection, which comprises the following steps:
(1) given commodity grade methionine is added in synthesizer, a certain amount of water and microelement metal is then added
Salt, and heat and be completely dissolved under the conditions of 80 DEG C~100 DEG C, methionine and microelement metal ion are according to molar ratio
It feeds intake for 1:1, then heats to 80 DEG C~105 DEG C, keep the temperature 0.5 hour to 2.0 hours, obtain methionine complexing metal salt
Aqueous solution；
(2) it is carried out directly after the methionine complexing metal saline solution that step (1) obtains being concentrated under reduced pressure into certain concentration again
Drying to constant weight, condensate water circulatory to step (1) water obtains methionine complexing metal product salt, the resultant metal after dry
The complexing rate of ion reaches 98% or more, and methionine complexing metal purity salt reaches 98% or more, the receipts of methionine complexing metal salt
Rate reaches 99% or more.
The molecular structural formula of its methionine complexing metal salt is as follows:
According to egg base acid complexing metal salt described in above-mentioned molecular structural formula by cationic egg base acid complexing metal and anion X group
At X is bisulfate ion, chloride ion or acetate ion, and metal ions M is copper ion, manganese ion, cobalt ions, nickel ion, three
One or more of valence chromium ion, when metal ion is the divalent ions such as copper ion, manganese ion, cobalt ions, nickel ion,
C is 1, a 1, and b 1, X are chloride ion, bisulfate ion or acetate；When metal ion is trivalent chromic ion, c 2, a 1,
B is that 2, X is chloride ion, bisulfate ion or acetate；
Further, methionine described in step (1), trace elements metal salt are feed grade or analyze pure commodity, described
Methionine be D, perhaps the L-type trace elements metal salt is solid or liquid, preferably solid microelement to L-type
The anhydrous compound of metal salt or hydrate containing the crystallization water.
Further, the trace elements metal salt is copper ion, manganese ion, cobalt ions, nickel ion, trivalent chromic ion
With the anhydrous compound of sulfate radical, chloride ion or acetate composition or containing the hydrate of the crystallization water.
Further, it is 1:1.5~8.0, preferably 1:1.5~6.0 that mass ratio, which is added, in methionine described in step (1) and water,
Particularly preferred 1:1.5~2.5；Methionine and metal ion molar ratio are 1.0, and the temperature of complex reaction is 80 DEG C~105
DEG C, preferably 85 DEG C~95 DEG C, particularly preferred 90 DEG C~95 DEG C, the complex reaction time is 0.5~2 hour, preferably 1~1.5 hour.
Further, dry described in step (2) be normal pressure forced air drying, one of be dried under reduced pressure, be spray-dried or
It is a variety of, preferably spray drying, spray drying inlet feed temperature be 60 DEG C~90 DEG C, preferably 70 DEG C~90 DEG C, particularly preferred 85
DEG C~90 DEG C.
Further, the gas of the spray drying is nitrogen, and the temperature of nitrogen is 80 DEG C~140 DEG C, preferably 90 DEG C~
125 DEG C, nitrogen and vapor are after refrigerated separation, nitrogen circulation to nitrogen heater recycled, condensate water circulatory to step
Suddenly (1) uses water.
Further, process units includes synthesizer, intermediate storage tank, spray drying tower, nitrogen heating device, gas-solid point
From device, nitrogen condensing unit and product storage device；
The synthesizer, intermediate storage tank, spray drying tower, gas-solid separating device, nitrogen condensing unit are sequentially connected；The conjunction
At being provided with material and water inlet on device；Nitrogen heating device, the nitrogen heating dress are provided on the spray drying tower
It installs and is equipped with nitrogen inlet；The spray drying tower, gas-solid separating device are connect with product storage device respectively；The nitrogen is cold
The nitrogen recycling of solidifying device is recycled in nitrogen heating device, and the recycling condensing water of nitrogen condensing unit is into synthesizer；
The synthesizer is for the complex reaction of selenomethionine and metal salt and the concentration of material；The intermediate storage tank
To store the reaction solution to be spray-dried；The spray drying tower is used to dry in synthesizer by the material of concentration；
The nitrogen heating device is used to heat the nitrogen being sent into spray-drying installation, and the gas-solid separating device is spraying for separating
Entrainment solid small particles product in dry discharge gas；The nitrogen condensing unit is in the dry discharge gas of cooling spray
Water.
Further, the synthesizer be glass reinforced plastic spray or the tank reactor of liner enamel, tower reactor or
One of micro passage reaction；The spray drying tower is pressure spray drying tower, air-stream spraying drying tower, centrifugal spray dryer
One of dry tower；The gas-solid separating device is gravity settling dust remover, cyclone separator, inertial dust separator or bag type filtering
One of device is a variety of.
Further, the nitrogen recycling recycling device includes sequentially connected gas-solid separator, deduster and nitrogen
Cooler, so-called gas-solid separator are connect with spray-drying installation, and the nitrogen cooler is connect with nitrogen heating device.
Further, the nitrogen recycling recycling device further includes intermediate storage mean, the intermediate storage dress
It sets and is connect with nitrogen cooler, for storing the liquid of refrigerated separation in nitrogen cooler；The process units further includes product
Storage device, the product storage device are connect with spray-drying installation.
The advantages and positive effects of the present invention are: the methionine complexing metal product salt and gold of (1) available high-purity
Belong to ion height complexing rate, product stability is high, is more suitable and uses as feed agent；(2) method of the invention has wiper ring
It protects, almost no three wastes generates, and is suitable for large-scale industrial production, can be continuously produced, and high income, production cost is low, and
Product avoids a large amount of dust pollution without pulverizing and sieving；(3) mobility can be obtained it is not necessary that carrier is added during the preparation process
Preferable product, product purity are high；(4) raw material sources used in are stable, cheap, product processes are simple, producing
In the process, pH value is adjusted without using sodium hydroxide or other alkali, no secondary salt product generates and a large amount of reluctant saliferous
Waste water generates, and has environment-protecting clean production technology characteristic；(5) without using initiator, save production cost and which reduce
The introducing of impurity, and avoid the need to make complex reaction completely and methionine is excessively used；(6) process and its device
With easy to operate, both can be continuously produced, can also intermittence production or semicontinuous half gap metaplasia produce, production dress
For simply and with maintenance.
Detailed description of the invention
Fig. 1 is methionine complexing metal salt operation system structure schematic diagram.
Specific embodiment
The present invention is described in further detail below by specific embodiment, it is not to limit that following embodiment, which is descriptive,
Property, this does not limit the scope of protection of the present invention.
The production procedure of process units system of the present invention is as follows:
Now methionine is added in inner lining glass fiber reinforced plastic or enamel synthesizer, then a certain amount of water is added into synthesizer
(or condensed water of recycled) then heats to certain temperature, stirring heat preservation a period of time.Into above-mentioned synthesizer
A certain amount of trace elements metal salt is added, under stirring, is heated to certain temperature, heat preservation a period of time, obtains one
Determine the methionine complexing metal reactant salt mixed liquor of concentration.Mixed liquor is obtained in a certain temperature conditions for obtained above, it should
Mixed liquor keeps good mobility.The mixed liquor is directly over spray-drying installation water removal, obtains methionine complexing metal salt
Finished product；Reaction mixture can also be collected to deposit in centre and carry out spray drying treatment in tank again.Methionine complexing after drying
Metal salt enters in product storage device, is then packed.The nitrogen tail gas excluded from spray drying first passes through gas solid separation
Abjection entrainment solid small particles product, then through moisture in nitrogen condensation removing, nitrogen is passed through spray-drying installation by heating again
Middle recycling, condensed water enter recycling and reusing in synthesizer.As shown in Figure 1.
1 D of embodiment, the preparation of L-Methionine complex cobalt sulfate
The complex reaction of D, L-Methionine and cobaltous sulfate: the D, L- of 301.01kg content 99wt% are added in the reaction kettle of 2000L
Methionine crystal (2000 moles) and deionized water 602.02kg, then heat to 85 DEG C, content are added while stirring
313.13kg(2000 moles of the anhydrous cobaltous sulfate of 99wt%), stirring is completely dissolved, and is warming up to 95 DEG C immediately, 1.0 hours are kept the temperature,
Obtain D, L-Methionine complex cobalt
Sulfate solution, D in the aqueous solution, L-Methionine complex cobalt sulfate concentration are 49.86wt%.
D, the spray drying treatment of L-Methionine complex cobalt sulfate: by D obtained above, L-Methionine complex cobalt sulfuric acid
Saline solution carries out concentration in complex reaction kettle, and reaction mixture is concentrated into concentration 80%, and the concentrate is in 90 DEG C of items
There is good mobility under part, then carry out spray drying treatment, nitrogen preheating temperature is 115 DEG C, at spray drying
The D obtained after reason, L-Methionine complex cobalt sulfate product 610.5kg, D, L-Methionine complex cobalt sulfate yield is >=
99.9%, product has good mobility, and product is pink powder shape, crosses 0.25mm pore analysis sieve, and product percent of pass is big
Cobalt content is 19.31wt% in 99%, product, and the complexing rate of cobalt is 99%, D, and L-Methionine complexing rate is 99%, D, L- in product
Methionine content is 48.81wt%.It is spray-dried methionine dissolution water of the condensate water circulatory of condensing recovery to lower batch, nitrogen
Gas is recycled to lower batch spray drying gas.
The preparation of 2 L-Methionine complex cobalt acetate of embodiment
The complex reaction of L-Methionine and cobalt acetate: the L- egg ammonia of 301.01kg content 99wt% is added in the reaction kettle of 2000L
Acid crystal (2000 moles) and the condensed water recycled of embodiment 1 and its deionized water added amount to 750kg, then heat to 85
DEG C, four 503.19kg(2000 moles of the cobalt acetates of hydration of content 99wt% are added while stirring), stirring is completely dissolved,
It is warming up to 95 DEG C immediately, keeps the temperature 1.0 hours, obtains L-Methionine complex cobalt acetate aqueous solution, L-Methionine in the aqueous solution
Complex cobalt acetate concentration is 34.25wt%.
The spray drying treatment of L-Methionine complex cobalt acetate: by L-Methionine complex cobalt acetic acid salt water obtained above
Solution carries out concentration in complex reaction kettle, and reaction mixture is concentrated into concentration 80%, and the concentrate is under the conditions of 90 DEG C
With good mobility, spray drying treatment is then carried out, nitrogen preheating temperature is 115 DEG C, after spray drying treatment
Obtained L-Methionine complex cobalt acetate production 535.36kg, L-Methionine complex cobalt acetate yield are >=99.9%, product
With good mobility, product is pink powder shape, crosses 0.25mm pore analysis sieve, and product percent of pass is greater than 99%, product
Middle cobalt content is 22.02wt%, and the complexing rate of cobalt is 99%, and L-Methionine complexing rate is 99%, and L-Methionine content is in product
55.66wt%.The condensate water circulatory of condensing recovery is spray-dried to the methionine dissolution water of lower batch, nitrogen circulation is to lower batch
Gas is used in secondary spray drying.
The preparation of chromium (III) chlorate is complexed in 3 D of embodiment, L-Methionine
The complex reaction of D, L-Methionine and chromium trichloride: being added the D of 301.01kg content 99wt% in the reaction kettle of 2000L,
The condensed water of L-Methionine crystal (2000 moles) embodiment 2 recycling circulation and the deionized water 752.50kg of supplement, then rise
319.92kg(2000 moles of the anhydrous chromium trichloride of content 99wt% is added to 85 DEG C in temperature while stirring), stirring is complete
Dissolution is warming up to 95 DEG C immediately, keeps the temperature 1.5 hours, obtains D, and chromium (III) chlorination saline solution, D, L- egg is complexed in L-Methionine
It is 39.62wt% that chromium (III) chlorination salinity, which is complexed, in propylhomoserin.
The spray drying treatment of chromium (III) chlorate is complexed in D, L-Methionine: by D obtained above, chromium is complexed in L-Methionine
(III) chlorination saline solution carries out reduced pressure processing in complex reaction kettle, and reaction mixture is concentrated into concentration 80wt%, should
Mixed liquor has good mobility under the conditions of 90 DEG C, then carries out spray drying treatment, and nitrogen preheating temperature is 105 DEG C,
Chromium (III) chlorination product salt 544.18kg, D, L-Methionine complexing is complexed in the D obtained after spray drying treatment, L-Methionine
Chromium (III) chlorate yield is 99.9%, and product has good mobility, and product is that aubergine is powdered, crosses the aperture 0.25mm
Analysis sieve, product percent of pass are greater than 99%, and chromium content is 19.11wt% in product, and the complexing rate of chromium is 99%.Spray drying condensation
Methionine dissolution water of the condensate water circulatory of recycling to lower batch, nitrogen circulation to lower batch spray drying gas.
The preparation of chromium (III) sulfate is complexed in 4 D of embodiment, L-Methionine
The complex reaction of D, L-Methionine and chromium sulfate: the D, L- of 301.01kg content 99wt% are added in the reaction kettle of 2000L
The condensed water 602.02kg of methionine crystal (2000 moles) and the recycling circulation of embodiment 3, then heats to 85 DEG C, in stirring
396.14kg(1000 moles of the anhydrous slufuric acid chromium of content 99wt% is added under state), stirring is completely dissolved, and is warming up to 95 immediately
DEG C, 1.5 hours are kept the temperature, D is obtained, chromium (III) sulfate solution, D is complexed in L-Methionine, and chromium (III) sulphur is complexed in L-Methionine
Hydrochlorate concentration is 45.76wt%.
The spray drying treatment of chromium (III) sulfate is complexed in D, L-Methionine: by D obtained above, chromium is complexed in L-Methionine
(III) sulfate solution carries out reduced pressure processing in complex reaction kettle, and reaction mixture is concentrated into concentration 78wt%, should
Mixed liquor has good mobility under the conditions of 90 DEG C, then carries out spray drying treatment, and nitrogen preheating temperature is 115 DEG C,
Chromium (III) is complexed in the D obtained after spray drying treatment, L-Methionine
Sulfate product 594.5kg, D, it is 99.9% that chromium (III) sulfate yield, which is complexed, in L-Methionine, and product has stream well
Dynamic property, product are that aubergine is powdered, cross 0.25mm pore analysis sieve, and product percent of pass is greater than 99%, trivalent chromium content in product
For 17.49wt%, the complexing rate of chromium is 99%.The methionine for being spray-dried condensate water circulatory to the lower batch of condensing recovery, which dissolves, to be used
Water, nitrogen circulation to lower batch spray drying gas.
Mn sulphate preparation is complexed in 5 D of embodiment, L-Methionine
D, L-Methionine and manganese sulfate complex reaction: the D of 301.01kg content 99wt%, L- egg are added in the reaction kettle of 2000L
Propylhomoserin crystal (2000 moles) and the condensed water recycled of embodiment 4 and the deionized water added amount to 602.02kg, then heat up
To 85 DEG C, 305.05kg(2000 moles of the anhydrous manganous sulfate of content 99wt% is added while stirring), stirring is completely molten
Solution is warming up to 95 DEG C immediately, keeps the temperature 1.5 hours, obtains D, and mn sulphate aqueous solution, D, L- in the aqueous solution is complexed in L-Methionine
The concentration that mn sulphate is complexed in methionine is 49.55wt%.
The spray drying treatment of mn sulphate is complexed in D, L-Methionine: by D obtained above, manganese sulfuric acid is complexed in L-Methionine
Saline solution carries out concentration in complex reaction kettle, and condensate water circulatory is dense by reaction mixture to lower batch industrial water
It is reduced to concentration 80wt%, which has good mobility under the conditions of 80 DEG C, then carries out spray drying treatment, nitrogen
Preheating temperature is 105 DEG C, the D obtained after spray drying treatment, and mn sulphate product 603.60kg is complexed in L-Methionine, is produced
Product are white powder, and product has good mobility, cross 0.25mm pore analysis sieve, and product percent of pass is greater than 99%, product
Middle manganese content is 18.22wt%, and the complexing rate of manganese is 99%；D, L-Methionine effectively complexing rate are 99%, D, and manganese is complexed in L-Methionine
The yield of sulfate is 99.8%, D in product, and L-Methionine mass percentage is 49.70wt%.It is spray-dried condensing recovery
Methionine dissolution water of the condensate water circulatory to lower batch, nitrogen circulation to lower batch spray drying gas.
The preparation of nickel sulfate is complexed in 6 D of embodiment, L-Methionine
D, L-Methionine and nickel sulfate complex reaction: the D of 301.01kg content 99wt%, L- egg are added in the reaction kettle of 2000L
The deionized water of propylhomoserin crystal (2000 moles) and 602.02kg, then heats to 85 DEG C, content is added while stirring
531.01kg(2000 moles of the six hydration nickel sulfate of 99wt%), stirring is completely dissolved, and is warming up to 95 DEG C immediately, heat preservation 1.0 is small
When, D is obtained, nickel sulfate solution is complexed in L-Methionine, and the concentration of D in the aqueous solution, L-Methionine complexing nickel sulfate are
42.39wt%。
Nickel sulfate spray drying treatment is complexed in D, L-Methionine: by D obtained above, nickel sulfate is complexed in L-Methionine
Aqueous solution carries out concentration in a kettle, and reaction mixture is concentrated into concentration 80wt%, and the concentrate is under the conditions of 90 DEG C
With good mobility, spray drying treatment is then carried out, nitrogen preheating temperature is 115 DEG C, after spray drying treatment
Nickel sulfate product 607.94kg, D is complexed in obtained D, L-Methionine, and it is >=99.9% that nickel sulfate yield, which is complexed, in L-Methionine,
Product has good mobility, and product is shallow green powder shape, crosses 0.25mm pore analysis sieve, and product percent of pass is greater than 99%,
Nickel content is 19.31wt% in product, and the complexing rate of nickel is 99%, D, and L-Methionine complexing rate is 99%, D in product, L-Methionine
Content is 49.02wt%.It is spray-dried methionine dissolution water of the condensate water circulatory of condensing recovery to lower batch, nitrogen circulation
To lower batch spray drying gas.
7 D of embodiment, the preparation of L-Methionine complex copper sulfate
D, L-Methionine and copper sulphate complex reaction: the D of 301.01kg content 99wt%, L- egg are added in the reaction kettle of 2000L
The deionized water of propylhomoserin crystal (2000 moles) and 602.02kg, then heats to 85 DEG C, content is added while stirring
505.05kg(2000 moles of the Salzburg vitriol of 99wt%), stirring is completely dissolved, and is warming up to 95 DEG C immediately, heat preservation 1.5 is small
When, obtain D, L-Methionine complex copper sulfate solution, D in the aqueous solution, the concentration of L-Methionine complex copper sulfate is
43.97wt%。
D, L-Methionine complex copper sulfate spray drying treatment: by D obtained above, L-Methionine complex copper sulfate
Aqueous solution carries out concentration, condensate water circulatory to lower batch industrial water, by D, L-Methionine complex copper sulphur in a kettle
Hydrochlorate reaction mixture is concentrated into concentration 80wt%, which has good mobility under the conditions of 70 DEG C, is then sprayed
Mist is dried, and nitrogen preheating temperature is 105 DEG C, the D obtained after spray drying treatment, L-Methionine complex copper sulfate
Product 621.90kg, product are that pewter is powdered, and product has good mobility, and copper content is 20.42wt% in product,
The complexing rate of copper is 99%, D, and the yield of L-Methionine complex copper sulfate is 99.7%.It is spray-dried the condensed water of condensing recovery
It is recycled to the methionine dissolution water of lower batch, nitrogen circulation to lower batch spray drying gas.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (9)
1. a kind of production method of the methionine complexing metal salt of clean and environmental protection, which comprises the following steps:
(1) given commodity grade methionine is added in synthesizer, then addition water and trace elements metal salt, and
It heats and is completely dissolved under the conditions of 80 DEG C~100 DEG C, methionine is 1:1 progress according to molar ratio with microelement metal ion
It feeds intake, then heats to 80 DEG C~105 DEG C, keep the temperature 0.5 hour to 2.0 hours, obtain methionine complexing metal saline solution；
(2) it is carried out directly after the methionine complexing metal saline solution that step (1) obtains being concentrated under reduced pressure into certain concentration again
Drying to constant weight, condensate water circulatory to step (1) water obtains methionine complexing metal product salt, the resultant metal after dry
The complexing rate of ion reaches 98% or more, and methionine complexing metal purity salt reaches 98% or more, the receipts of methionine complexing metal salt
Rate reaches 99% or more.
2. a kind of production method of the methionine complexing metal salt of clean and environmental protection according to claim 1, which is characterized in that
The molecular structural formula of the methionine complexing metal salt is as follows:
According to egg base acid complexing metal salt described in above-mentioned molecular structural formula by cationic egg base acid complexing metal and anion X group
At X is bisulfate ion, chloride ion or acetate ion, and metal ions M is copper ion, manganese ion, cobalt ions, nickel ion, three
One or more of valence chromium ion, when metal ion is the divalent ions such as copper ion, manganese ion, cobalt ions, nickel ion,
C is 1, a 1, and b 1, X are chloride ion, bisulfate ion or acetate；When metal ion is trivalent chromic ion, c 2, a 1,
B is that 2, X is chloride ion, bisulfate ion or acetate.
3. a kind of production method of the methionine complexing metal salt of clean and environmental protection according to claim 1, which is characterized in that
Methionine described in step (1), trace elements metal salt are feed grade or the pure commodity of analysis, and the methionine is D, L-
Type perhaps the L-type trace elements metal salt be solid or liquid,.
4. a kind of production method of the methionine complexing metal salt of clean and environmental protection according to claim 1,2 or 3, feature
It is, the trace elements metal salt is copper ion, manganese ion, cobalt ions, nickel ion, trivalent chromic ion and sulfate radical, chlorine
The anhydrous compound that ion or acetate form or the hydrate containing the crystallization water.
5. special according to a kind of described in any item production methods of the methionine complexing metal salt of clean and environmental protection of claim 4
Sign is that mass ratio is added as 1:1.5~8.0 in methionine described in step (1) and water；Methionine and metal ion feed intake mole
Than being 1.0, the temperature of complex reaction is 80 DEG C~105 DEG C, and the complex reaction time is 0.5~2 hour.
6. a kind of production method of the methionine complexing metal salt of clean and environmental protection according to claim 1, which is characterized in that
It is dry described in step (2) be normal pressure forced air drying, one or more of be dried under reduced pressure, be spray-dried.
7. a kind of production method of the methionine complexing metal salt of clean and environmental protection according to claim 5, which is characterized in that
The gas of the spray drying is nitrogen, and the temperature of nitrogen is 80 DEG C~140 DEG C, nitrogen and vapor after refrigerated separation,
Nitrogen circulation to nitrogen heater recycled, condensate water circulatory to step (1) uses water.
8. a kind of production method of the methionine complexing metal salt of clean and environmental protection according to claim 1, which is characterized in that
Its process units includes synthesizer, intermediate storage tank, spray drying tower, nitrogen heating device, gas-solid separating device, nitrogen condensation
Device and product storage device；
The synthesizer, intermediate storage tank, spray drying tower, gas-solid separating device, nitrogen condensing unit are sequentially connected；The conjunction
At being provided with material and water inlet on device；Nitrogen heating device, the nitrogen heating dress are provided on the spray drying tower
It installs and is equipped with nitrogen inlet；The spray drying tower, gas-solid separating device are connect with product storage device respectively；The nitrogen is cold
The nitrogen recycling of solidifying device is recycled in nitrogen heating device, and the recycling condensing water of nitrogen condensing unit is into synthesizer；
The synthesizer is for the complex reaction of selenomethionine and metal salt and the concentration of material；The intermediate storage tank
To store the reaction solution to be spray-dried；The spray drying tower is used to dry in synthesizer by the material of concentration；
The nitrogen heating device is used to heat the nitrogen being sent into spray-drying installation, and the gas-solid separating device is spraying for separating
Entrainment solid small particles product in dry discharge gas；The nitrogen condensing unit is in the dry discharge gas of cooling spray
Water.
9. process units according to claim 8, which is characterized in that the synthesizer is glass reinforced plastic spraying or liner
One of tank reactor, tower reactor or micro passage reaction of enamel；The spray drying tower is dry for press atomization
One of dry tower, air-stream spraying drying tower, centrifugal spray drying tower；The gas-solid separating device be gravity settling dust remover,
One of cyclone separator, inertial dust separator or bag filter are a variety of.
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| CN111978221A (en) * | 2020-08-18 | 2020-11-24 | 宁夏紫光天化蛋氨酸有限责任公司 | Preparation method of feed additive DL-methionine complex copper |
| CN112028783A (en) * | 2020-08-25 | 2020-12-04 | 重庆森乐美生物科技有限公司 | Production system and method of glycine complex nickel salt |
| CN112028782A (en) * | 2020-08-25 | 2020-12-04 | 重庆森乐美生物科技有限公司 | Production system and method of glycine complex chromium salt |
| CN115260068A (en) * | 2022-07-20 | 2022-11-01 | 天宝动物营养科技股份有限公司 | Divalent metal eutectic compound taking hydroxy methionine as film base and preparation method and application thereof |
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| CN115260068A (en) * | 2022-07-20 | 2022-11-01 | 天宝动物营养科技股份有限公司 | Divalent metal eutectic compound taking hydroxy methionine as film base and preparation method and application thereof |
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Application publication date: 20190820 |