CN106699544B - A kind of preparation method of propionic acid ammonium crystal and its pulvis - Google Patents
A kind of preparation method of propionic acid ammonium crystal and its pulvis Download PDFInfo
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- CN106699544B CN106699544B CN201510770377.XA CN201510770377A CN106699544B CN 106699544 B CN106699544 B CN 106699544B CN 201510770377 A CN201510770377 A CN 201510770377A CN 106699544 B CN106699544 B CN 106699544B
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- XJMWHXZUIGHOBA-UHFFFAOYSA-N azane;propanoic acid Chemical compound N.CCC(O)=O XJMWHXZUIGHOBA-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000013078 crystal Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 219
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 127
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 109
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 61
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 61
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 230000004044 response Effects 0.000 claims abstract description 6
- 230000002459 sustained effect Effects 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000010923 batch production Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 abstract description 28
- 230000008569 process Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 64
- 238000010521 absorption reaction Methods 0.000 description 48
- 238000012360 testing method Methods 0.000 description 23
- 238000001228 spectrum Methods 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- -1 organic acid salt Chemical class 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000019629 palatability Nutrition 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 206010011409 Cross infection Diseases 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- 206010029803 Nosocomial infection Diseases 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001046 anti-mould Effects 0.000 description 1
- 239000002546 antimould Substances 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000002072 distortionless enhancement with polarization transfer spectrum Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 206010022000 influenza Diseases 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation method of propionic acid ammonium crystal, includes the following steps: that propionic acid 1) is sequentially added first reactor, second reactor, third reactor, the propionic acid in first reactor and second reactor is stirred；2) liquefied ammonia is carried out to preheating and pressure stabilizing after evaporating separation, impurity removal matter；3) ammonia after preheating and pressure stabilizing first reactor is passed through to react；4) cooling control reaction temperature, pressure stabilizing；5) sustained response 1h or more opens third reactor, cools；6) propionic acid ammonium content in secondary amine device for absorbing tail gas is measured after the reaction was continued 2h-2.5h；7) stop logical ammonia, stir appropriate time, obtain propionic acid ammonium crystal.Also disclose a kind of preparation method of propionic acid ammonium pulvis, method and process is simple, efficiently, environmental protection, propionic acid ammonium crystal purity obtained, high income are propionic acid ammonium powder odorlessness, corrosion-free, agreeable to the taste good, high-efficient.
Description
Technical field
The invention belongs to field of chemical raw material preparation, and in particular to the preparation method of a kind of propionic acid ammonium crystal and its pulvis.
Background technique
As the fast development of feed industry, scale are grown, it is desirable that feed has higher quality and freshness, but feed
It is faced with during production, transport, storage and feeding etc. as Moisture in Feed is uneven, is exposed to the sun, heavy rain；Plum rains season, typhoon season etc.
The influence of weather conditions and frequently changeable influenza factor leads to feed moldy metamorphism, and then generates toxin, quality decline.
To prevent feed mouldy, most economical, easy and effective method is addition Midew preventive for feed, but most
Mould inhibitor is having more or less drawback using upper: toxicity, corrosivity, smell, influence palatability, cost performance be not high.No
It is disconnected to design and develop a kind of non-toxic, non-corrosive, odorlessness, do not influence being applied to for palatability, cost performance height and safety and environmental protection
The fresh-keeping additive of feedstuff mildew has particularly important realistic meaning.
Propionic acid ammonium is a kind of extremely strong substance of hygroscopicity, and main application is used as anti-corrosion, mould inhibitor, under the premise of acidity
Free propionic acid is generated, there is antibiotic property, to the special efficacy that has for preventing flavatin, and it is nearly unavailable to yeast, to all kinds of
Mould, gram-Negative bacillus effect are good, and the lower anti-corrosion effect of pH value is better, and anti-for feed or cereal goes rotten and anti-
Agglomeration has good effect.Above-described market and reality are needed, propionic acid ammonium has important Development volue.But due to third
Facile hydrolysis, the moisture absorption and the slightly higher temperature of sour ammonium dissolve characteristic, and what itself was participated in addition is weak acid and weak base reaction, more become to terminal
In difficulty, technique is cumbersome, increases cost, and be difficult purification, yield reduces, therefore find a kind of purity is high, high income and technique
Simply, the preparation process of low-cost propionic acid ammonium is this field thing very urgent at present.
Summary of the invention
For this purpose, technical problem to be solved by the present invention lies in overcome the preparation process of propionic acid ammonium in the prior art not at
Ripe, complex process, with high costs and product obtained are difficult the very low technical bottleneck of purification, yield, to propose a kind of purity
The preparation process of high, high income and simple process, low-cost propionic acid ammonium crystal and its pulvis.
In order to solve the above technical problems, the technical solution of the present invention is as follows:
The present invention provides a kind of preparation method of propionic acid ammonium crystal, and described method includes following steps:
1) propionic acid is sequentially added into sequentially connected first reactor, second reactor, third reactor, and anti-to first
The propionic acid in device and second reactor is answered to be stirred；
2) liquefied ammonia is carried out to preheating and pressure stabilizing after evaporating separation, impurity removal matter；
3) ammonia through separation, preheating and pressure stabilizing in step 2) is passed through first reactor, with third in first reactor
Acid reacts under stiring；
4) the cooling first reactor and second reactor, control reaction temperature, and carry out pressure stabilizing again；
5) after pressure stabilizing, sustained response 1h or more, ammonia is spilled over to second reactor in first reactor, with second reactor
Interior propionic acid reaction increases temperature in second reactor, opens third reactor, and cool down；
6) ammonia is spilled over to third reactor in second reactor after the reaction was continued 2-2.5h, with third in third reactor
Acid reaction increases third reactor temperature, measures the content of propionic acid ammonium in propionic acid liquid in third reactor；
7) stop being passed through ammonia, continue after stirring a period of time, take out product, sealing, cooling preservation, it is brilliant to obtain propionic acid ammonium
Body.
Preferably, the mixing speed of the stir process is 45r/min-50r/min in the step 1).
Preferably, it is 0.6MPa-1.2MPa that ammonia, which evaporates separating pressure, in the step 2)；Temperature reaches after the pre-heat treatment
To 40 DEG C -60 DEG C；After pressure stabilizing, ammonia pressure 0.6MPa-1.2MPa.
Preferably, the reaction temperature is 110 DEG C -130 DEG C, and ammonia pressure is after pressure stabilizing in the step 4)
0.6MPa-1.2MPa。
Preferably, the content of propionic acid ammonium accounts for the propionic acid liquid and propionic acid ammonium mixture in propionic acid liquid in the step 6)
The 10%-15% of quality.
Preferably, further including that will be overflowed not in the first reactor and the second reactor after the step 6)
It participates in reacting and remaining ammonia leads in fresh propionic acid solution and carries out down series-produced step.
Preferably, further including replacing the propionic acid liquid in the second reactor in described first after the step 7)
Propionic acid liquid storage in third reactor is used to prepare down the step of criticizing propionic acid ammonium by reactor.
Preferably, the heat source temperature of the warm in the step 2) is 75-85 DEG C, by tap water and participate in cold
But high-temperature water is mixed to get.
Preferably, propionic acid additional amount is every 1m in first reactor described in the step 1)3Middle addition 600kg-
700kg；Propionic acid additional amount is every 1m in the second reactor and third reactor3Middle addition 700kg-800kg.
The present invention also provides a kind of preparation method of propionic acid ammonium pulvis, include the following steps: 60-75 parts by weight propionic acid ammonium
Crystal and 25-40 parts by weight activated silica carrier are crushed to -100 mesh of 80 mesh after being uniformly mixed, drying again, after sieving
To obtain the final product.
The above technical solution of the present invention has the following advantages over the prior art:
(1) preparation method of propionic acid ammonium crystal provided by the invention, this method simple process, efficient, environmental protection, the first reaction
The production for lower batch of propionic acid ammonium can be recycled in unreacted propionic acid liquid in device, second reactor and third reactor, final extra
Another part tail ammonia out absorbs propionic acid liquid, and being synthesized adjusting again, can be made as low content propionic acid ammonium, high-content propionic acid structure anti-
Mould dose, lossless and waste；This reaction is exothermic reaction, and the heat of releasing is but also as the heat source for evaporating, preheating for liquefied ammonia；System
Propionic acid ammonium purity is high, high income, low in cost.
(2) preparation method of propionic acid ammonium pulvis provided by the invention, propionic acid ammonium pulvis obtained effect when it is exclusive continue,
Sustained release, thorough advantageous feature are odorlessness, corrosion-free, agreeable to the taste good, high-efficient.
Detailed description of the invention
In order to make the content of the present invention more clearly understood, it below according to specific embodiments of the present invention and combines
Attached drawing, the present invention is described in further detail, wherein
The infrared spectrogram of Fig. 1 propionic acid ammonium crystal prepared by the present invention；
Fig. 2 propionic acid ammonium crystal prepared by the present invention hydrogen nuclear magnetic resonance (1H) spectrogram；
Fig. 3 propionic acid ammonium crystal prepared by the present invention hydrogen nuclear magnetic resonance carbon (13C) spectrogram；
The hydrogen nuclear magnetic resonance DEPT135 spectrogram of Fig. 4 propionic acid ammonium crystal prepared by the present invention；
The hydrogen nuclear magnetic resonance DEPT90 spectrogram of Fig. 5 propionic acid ammonium crystal prepared by the present invention；
The ESI mass spectrogram of Fig. 6 propionic acid ammonium crystal prepared by the present invention.
Specific embodiment
Embodiment 1
The present embodiment is used to illustrate the preparation method of propionic acid ammonium crystal provided by the invention.Steps are as follows:
1) volume is added in 600kg propionic acid is 1m3First reactor, 700kg propionic acid be added volume be 1m3It is second anti-
Answering device, 700kg propionic acid that volume is added is 1m3Third reactor in, the first reactor be main reaction unit, described second
Reactor is level-one ammonia device for absorbing tail gas, and the third reactor is secondary amine absorption plant, the main reaction device, level-one
Ammonia device for absorbing tail gas and secondary amine device for absorbing tail gas are sequentially connected with；And to main reaction device and level-one ammonia device for absorbing tail gas
In propionic acid be stirred；In the present embodiment, the main reaction device is main reaction kettle, and level-one ammonia device for absorbing tail gas is level-one
Ammonia tail gas absorption kettle, secondary amine device for absorbing tail gas are secondary amine tail gas absorption kettle；Start main reaction kettle and level-one ammonia tail gas is inhaled
Stirring motor power supply in kettle is received, then is adjusted by frequency converter stir axle speed in two kettles respectively, making agitating paddle, (axis stream, dispersion are stirred
Mix paddle) speed in 45r/min；
2) liquefied ammonia in ammonia tank is isolated at 0.6MPa to wherein micro entrained oil class and machine through ammonia vapor seperator
Tool impurity enters back into ammonia preheater and is preheated to 40 DEG C, and the heat source temperature of the ammonia preheater is 75 DEG C, by tap water and participation
Cooling high-temperature water is mixed to get, and is stablized by adjusting valve regulation ammonia pressure in 0.6MPa；
3) pre-separated, preheating and pressure stabilizing ammonia, then slowly opens the air valve into main reaction kettle, make ammonia at the uniform velocity into
Reaction kettle is become owner of, and disperses propionic acid liquid Xiangli for ammonia, gas-liquid exothermic reaction occurs for stirring under the speed of 45r/min；
4) main reaction kettle and the matched cooling tower of level-one ammonia tail gas absorption kettle are opened simultaneously, is dropped through cooling circulating water is cooling
Temperature controls reaction temperature finally at 110 DEG C, reconciles ammonia pressure again to 0.6MPa；
5) after pressure stabilizing, sustained response 1h or more, ammonia is spilled over to level-one ammonia tail gas absorption kettle in main reaction kettle, with level-one ammonia
Propionic acid reaction in tail gas absorption kettle increases level-one ammonia tail gas absorption temperature in the kettle, opens secondary amine tail gas absorption kettle, goes forward side by side
Row cools；
6) ammonia is spilled over to secondary amine tail gas absorption kettle in the reaction was continued 2h rear stage ammonia tail gas absorption kettle, with secondary amine tail
Propionic acid reaction in aspiration kettle increases secondary amine tail gas absorption temperature in the kettle, measures secondary amine tail gas using fast titration method
In absorption kettle in propionic acid liquid propionic acid ammonium content, the content of propionic acid ammonium accounts for the propionic acid liquid and propionic acid ammonium mixture in the present embodiment
The 10% of quality；Stopping is passed through ammonia, prevents ammonia into main reaction kettle valve, is stirred for reaction about 5min, then that the master is anti-
It answers to have neither part nor lot in kettle and the level-one ammonia tail gas absorption kettle and react and remaining ammonia leads in fresh propionic acid solution and criticize
Production；
7) under cooled conditions, main reaction kettle continues stirring a period of time, takes out product, cooling preservation, detection, packet
Dress is to get propionic acid ammonium crystal；Then the propionic acid liquid in the level-one ammonia tail gas absorption kettle is replaced in the main reaction kettle, by two
Propionic acid liquid storage in grade ammonia tail gas absorption kettle is used to prepare down batch propionic acid ammonium.
Embodiment 2
The present embodiment is used to illustrate the preparation method of propionic acid ammonium crystal provided by the invention.Steps are as follows:
1) volume is added in 650kg propionic acid is 1m3First reactor, 750kg propionic acid be added volume be 1m3It is second anti-
Answering device, 750kg propionic acid that volume is added is 1m3Third reactor in, the first reactor be main reaction unit, described second
Reactor is level-one ammonia device for absorbing tail gas, and the third reactor is secondary amine absorption plant, the main reaction device, level-one
Ammonia device for absorbing tail gas and secondary amine device for absorbing tail gas are sequentially connected with；And to main reaction device and level-one ammonia device for absorbing tail gas
In propionic acid be stirred；In the present embodiment, the main reaction device is main reaction kettle, and level-one ammonia device for absorbing tail gas is level-one
Ammonia tail gas absorption kettle, secondary amine device for absorbing tail gas are secondary amine tail gas absorption kettle；Start main reaction kettle and level-one ammonia tail gas is inhaled
Stirring motor power supply in kettle is received, then is adjusted by frequency converter stir axle speed in two kettles respectively, making agitating paddle, (axis stream, dispersion are stirred
Mix paddle) speed in 48r/min；
2) liquefied ammonia in ammonia tank is isolated at 1MPa to wherein micro entrained oil class and machinery through ammonia vapor seperator
Impurity enters back into ammonia preheater and is preheated to 50 DEG C, and the heat source temperature of the ammonia preheater is 80 DEG C, by tap water and is participated in cold
But high-temperature water is mixed to get, and is stablized by adjusting valve regulation ammonia pressure in 1MPa；
3) pre-separated, preheating and pressure stabilizing ammonia, then slowly opens the air valve into main reaction kettle, make ammonia at the uniform velocity into
Reaction kettle is become owner of, and disperses propionic acid liquid Xiangli for ammonia, gas-liquid exothermic reaction occurs for stirring under the speed of 47r/min；
4) main reaction kettle and the matched cooling tower of level-one ammonia tail gas absorption kettle are opened simultaneously, is dropped through cooling circulating water is cooling
Temperature controls reaction temperature finally at 120 DEG C, reconciles ammonia pressure again to 1MPa；
5) after pressure stabilizing, sustained response 1h or more, ammonia is spilled over to level-one ammonia tail gas absorption kettle in main reaction kettle, with level-one ammonia
Propionic acid reaction in tail gas absorption kettle increases level-one ammonia tail gas absorption temperature in the kettle, opens secondary amine tail gas absorption kettle, goes forward side by side
Row cools；
6) ammonia is spilled over to secondary amine tail gas absorption kettle in the reaction was continued 2.2h rear stage ammonia tail gas absorption kettle, with secondary amine
Propionic acid reaction in tail gas absorption kettle increases secondary amine tail gas absorption temperature in the kettle, measures secondary amine tail using fast titration method
In aspiration kettle in propionic acid liquid propionic acid ammonium content, the content of propionic acid ammonium accounts for the propionic acid liquid and mixes with propionic acid ammonium in the present embodiment
The 12% of amount of substance；Stopping is passed through ammonia, prevents ammonia into main reaction kettle valve, reaction about 5min is stirred for, then by the master
It has neither part nor lot in and reacts and remaining ammonia leads in fresh propionic acid solution and carries out down in reaction kettle and the level-one ammonia tail gas absorption kettle
Criticize production；
7) under cooled conditions, main reaction kettle continues stirring a period of time, takes out product, cooling preservation, detection, packet
Dress is to get propionic acid ammonium crystal；Then the propionic acid liquid in the level-one ammonia tail gas absorption kettle is replaced in the main reaction kettle, by two
Propionic acid liquid storage in grade ammonia tail gas absorption kettle is used to prepare down batch propionic acid ammonium.
Embodiment 3
The present embodiment is used to illustrate the preparation method of propionic acid ammonium crystal provided by the invention.Steps are as follows:
1) volume is added in 700kg propionic acid is 1m3First reactor, 800kg propionic acid be added volume be 1m3It is second anti-
Answering device, 800kg propionic acid that volume is added is 1m3Third reactor in, the first reactor be main reaction unit, described second
Reactor is level-one ammonia device for absorbing tail gas, and the third reactor is secondary amine absorption plant, the main reaction device, level-one
Ammonia device for absorbing tail gas and secondary amine device for absorbing tail gas are sequentially connected with；And to main reaction device and level-one ammonia device for absorbing tail gas
In propionic acid be stirred；In the present embodiment, the main reaction device is main reaction kettle, and level-one ammonia device for absorbing tail gas is level-one
Ammonia tail gas absorption kettle, secondary amine device for absorbing tail gas are secondary amine tail gas absorption kettle；Start main reaction kettle and level-one ammonia tail gas is inhaled
Stirring motor power supply in kettle is received, then is adjusted by frequency converter stir axle speed in two kettles respectively, making agitating paddle, (axis stream, dispersion are stirred
Mix paddle) speed in 50r/min；
2) liquefied ammonia in ammonia tank is isolated at 1.2MPa to wherein micro entrained oil class and machine through ammonia vapor seperator
Tool impurity enters back into ammonia preheater and is preheated to 60 DEG C, and the heat source temperature of the ammonia preheater is 85 DEG C, by tap water and participation
Cooling high-temperature water is mixed to get, and is stablized by adjusting valve regulation ammonia pressure in 1.2MPa；
3) pre-separated, preheating and pressure stabilizing ammonia, then slowly opens the air valve into main reaction kettle, make ammonia at the uniform velocity into
Reaction kettle is become owner of, and disperses propionic acid liquid Xiangli for ammonia, gas-liquid exothermic reaction occurs for stirring under the speed of 50r/min；
4) main reaction kettle and the matched cooling tower of level-one ammonia tail gas absorption kettle are opened simultaneously, is dropped through cooling circulating water is cooling
Temperature controls reaction temperature finally at 130 DEG C, reconciles ammonia pressure again to 1.2MPa；
5) after pressure stabilizing, sustained response 1h or more, ammonia is spilled over to level-one ammonia tail gas absorption kettle in main reaction kettle, with level-one ammonia
Propionic acid reaction in tail gas absorption kettle increases level-one ammonia tail gas absorption temperature in the kettle, opens secondary amine tail gas absorption kettle, goes forward side by side
Row cools；
6) ammonia is spilled over to secondary amine tail gas absorption kettle in the reaction was continued 2h rear stage ammonia tail gas absorption kettle, with secondary amine tail
Propionic acid reaction in aspiration kettle increases secondary amine tail gas absorption temperature in the kettle, measures secondary amine tail gas using fast titration method
In absorption kettle in propionic acid liquid propionic acid ammonium content, the content of propionic acid ammonium accounts for the propionic acid liquid and propionic acid ammonium mixture in the present embodiment
The 15% of quality；Stopping is passed through ammonia, prevents ammonia into main reaction kettle valve, is stirred for reaction about 5min, then that the master is anti-
It answers to have neither part nor lot in kettle and the level-one ammonia tail gas absorption kettle and react and remaining ammonia leads in fresh propionic acid solution and criticize
Production；
7) under cooled conditions, main reaction kettle continues stirring a period of time, takes out product, cooling preservation, detection, packet
Dress is to get propionic acid ammonium crystal；Then the propionic acid liquid in the level-one ammonia tail gas absorption kettle is replaced in the main reaction kettle, by two
Propionic acid liquid storage in grade ammonia tail gas absorption kettle is used to prepare down batch propionic acid ammonium.
Embodiment 4
The present embodiment is for illustrating propionic acid ammonium pulvis preparation method provided by the invention.Steps are as follows:
Any obtained 60 parts by weight of propionic acid ammonium crystal of embodiment 1-3 are stirred with 40 parts by weight activated silica carriers
It is crushed to 80 mesh again after mixing uniformly mixed, drying, sieving is examined, packed to get the propionic acid ammonium pulvis that feed can directly be added.
Embodiment 5
Any obtained 70 parts by weight of propionic acid ammonium crystal of embodiment 1-3 are stirred with 30 parts by weight activated silica carriers
It is crushed to 90 mesh again after mixing uniformly mixed, drying, sieving is examined, packed to get the propionic acid ammonium pulvis that feed can directly be added.
Embodiment 6
Any obtained 75 parts by weight of propionic acid ammonium crystal of embodiment 1-3 are stirred with 25 parts by weight activated silica carriers
It is crushed to 100 mesh again after mixing uniformly mixed, drying, sieving is examined, packed to get the propionic acid ammonium pulvis that feed can directly be added.
Experimental example
Experimental example 1
This experimental example is for illustrating propionic acid ammonium pulvis provided by the invention (being made by 4 the method for embodiment) and other classes
Type mould inhibitor Piglet s colibacillosis.
1. test material and method
1.1 test material
1.1.1 it tests and uses feed: baby pig feedstuff moisture content 13.25% (Condar your feed corporation,Ltd in Dongguan provides)
Feed ingredient is used in the test of table 1
| Corn | Barley | Mai Fupi | Rape cake | Continuous seedcake | Conch meal | Salt | It is total |
| 37.0 | 34.5 | 9.0 | 8.0 | 10.0 | 1.0 | 0.5 | 100 |
1.1.2 mould inhibitor is used in test
Table 2 test mould inhibitor recipe ingredient and weight percent
1.2.1 test method
1.2.1 test grouping and design
This experiment points six groups and a control group totally seven groups,
Every group with 10 kilograms of above-mentioned pig starter feed, is added 0.12% (i.e. every group of addition that mould proof agent dose is feed relative
1.2 grams of above-mentioned test mould inhibitor), it is sufficiently mixed uniformly, prevents the cross-infection of different tests group, be pair not add mould inhibitor
It according to group, is respectively charged into clear PE bag and seals, be placed in 30-35 DEG C, stood under the environmental condition of relative humidity 75% or so (to prevent
Move and seethe feed flowing and being not easy observation or observation result has error), observation is primary weekly, and record agglomerates and mouldy time.
2.1 loggings are shown in Table 3
3 logging table of table
| Number of days | 7 | 14 | 21 | 28 | 35 | 42 | 49 | 56 | 63 | 70 | 77 | 84 | 91 | 98 |
| Mould inhibitor | ||||||||||||||
| A group | - | - | - | - | - | - | - | - | - | - | -● | + | ++ | ++ |
| B group | - | - | - | - | - | - | - | -● | ± | ++ | +++ | ☉ | ||
| C group | - | - | - | - | +● | ++ | +++ | ☉ | ||||||
| D group | - | - | - | +● | ++ | +++ | ☉ | |||||||
| E group | - | - | +● | ++ | +++ | ☉ | ||||||||
| F group | - | - | - | ±● | ++ | +++ | ☉ | |||||||
| G group | - | +● | ++ | +++ | ☉ |
2.2 moulding abilities measurement foundation is shown in Table 4
4 moulding ability measurement result of table and according to explanation
3. results and discussion
It is obtained by above-mentioned test result, for tried pig starter feed in moisture content 13.25%, temperature is 30-35 DEG C, relatively wet
Degree is obviously more mouldy than control group delay added with the mould inhibitor group of 0.12% dosage to store under the conditions of 75% or so environment, upper
It states in a few class mould inhibitors of test, in terms of anti-mold effect, mildew speed and moulding ability: worst is E group natural plant kind, 21
It gathers mould and agglomerates, and mildew speed is fast；Secondly D group organic acid salt, start within 28 days agglomeration and it is mouldy, go mouldy speed it is fast；
It is that F is assembled with organic acid, acylate and other components again, gather mould agglomeration after 28 days；The single B group and third for having propionic acid
Acid compounds C group with glacial acetic acid and compares, and the mould proof time is slightly longer, illustrates that propionic acid is better than glacial acetic acid, once feed mold, speed
Accelerate.
4 test result of A group embodiment of the present invention and other group compare, the mould proof time and mildew speed on, better than its
He is five groups, and under equal conditions feed storage A group embodiment 4 starts to agglomerate for fresh-keeping 77 days, gathers mould within 84 days, and speed of going mouldy
It is relatively slow.
Experimental example 2
Propionic acid ammonium pulvis synthesized by 4-6 of the embodiment of the present invention, sanitary index requirement: total arsenic (As)≤0.0008%,
Heavy metal (in terms of Pb)≤0.0011% and fluorine (F)≤0.06%.To prepared product sanitary index testing result involved in the present invention
It is as follows:
(1) measurement of total arsenic (As):
(measuring method: GB/T 13079-2006 hydride generation atomic fluorescence photometry)
Instrument: Atomic Fluorescence Spectrometer (model: AF-640A): Beijing North divides Rayleigh analysis instrument company；Be not detected (<
0.0001)。
(2) measurement of heavy metal (in terms of Pb):
(measuring method: GB/T 13080-2004 sample dissolution-dry ashing method)
Instrument: atomic absorption spectrophotometer (model: WFX-310): Beijing North divides Rayleigh analysis instrument company；It is not detected
(<0.0001)。
(3) measurement of fluorine (F):
(measuring method: GB/T 13083-2002 fluorescence spectrophotometric method)
Instrument: acidometer (model PHSJ-3F): Shanghai instrument electricity Scientific Instruments Corporation；Electrode: 232 type calomel electrodes, PF-1
Type fluoride ion selective electrode (measurement range 10-1Mol/L~5 × 10-7mol/L).Measurement result 0.00014%.
Through detecting, as a result meet national health index.
Experimental example 3
Propionic acid ammonium crystal synthesized by the embodiment of the present invention 2 uses infrared (IR), nuclear magnetic resonance (NMR) and mass spectrum (ESI)
Technology is tested and is characterized to it, as a result as follows:
(1) infrared (IR) spectrum test (detection foundation are as follows: JY/T001-1996)
Instrument: Fourier transformation infrared spectrometer (model: WQF-520A) Beijing Rayleigh spectral instrument company
Test condition: KBr pressed disc method
Test result is as follows:
1, the infrared spectrogram of the sample is shown in attached drawing 1.
2, spectral characterization is as follows:
a、1403cm-1, it is NH4 +Bending vibration absorption peak；
b、1556cm-1, it is carboxylate anion stretching vibration absworption peak；
c、2983cm-1, it is methylmethylene stretching vibration absworption peak；
d、3149cm-1, it is N-H stretching vibration absworption peak.
(2) nuclear magnetic resonance (NMR) test (detection foundation are as follows: JY/T007-1996)
Instrument: superconducting pulse fourier transform nuclear magnetic resonance spectrometer, (model: Bruker DRX-400,400MHz) Germany.
Test condition: solvent: DMSO-d6；
Reference substance: TMS；
Temperature: 20 DEG C；
Frequency:1H spectrum: 400.130MHz；13C spectrum: 100.613MHz.
Test result: 1, sample test hydrogen nuclear magnetic resonance (1H) spectrum, carbon (13C) spectrum, DEPT135 and DEPT90 spectrum, point
Attached drawing 2, attached drawing 3, attached drawing 4 and attached drawing 5 are not seen.
2, spectral characterization is as follows:
A, hydrogen (1H it) composes；
The CH that δ 0.934 (3H, t, 7.6) is 3 in spectrum3Proton peak, δ 2.017 (2H, q, 7.6) are 2 CH2Proton peak, δ
6.215 (4H, s, 9.2) are the proton peak of active hydrogen (referring to following structural formula).
B, carbon (13C) spectrum, DEPT spectrum
Carbon spectrum shows 3 carbon peaks, and DEPT135, which is composed, has showed 1 posivtive spike and 1 negative peak, and DEPT90 spectrum is without appearance, and 3
Spectrum combines, it may be determined that the δ 10.6 in carbon spectrum is 3 CH3Carbon peak, δ 30.0 are 2 CH2Carbon peak, δ 177.7 are 1 carbonyl carbon peak
(referring to above structure formula).
(3) mass spectrum (ESI) test (detection foundation are as follows: JY/T003-1996)
Instrument: triple quadrupole bar liquid chromatograph-mass spectrometer (model: TSQ Quantum Ultra)
Test condition: spray voltage: -3.0kV；Source heating temperature: 200 DEG C；Capillary temperature: 300 DEG C；Sheath gas:
30arb；Secondary air speed: 5arb.
Test result: 1, the ESI mass spectrogram of the sample is shown in attached drawing 6.
2, spectral characterization is as follows:
A, M/Z 91 is M+·；
B, M/Z 73 is CH3CH2COO-。
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (3)
1. a kind of preparation method of propionic acid ammonium crystal, which is characterized in that described method includes following steps:
1) propionic acid is sequentially added into sequentially connected first reactor, second reactor, third reactor, and to first reactor
It is stirred with the propionic acid in second reactor；
2) liquefied ammonia is carried out to preheating and pressure stabilizing after evaporating separation, impurity removal matter；The pressure of liquefied ammonia evaporation separation, impurity removal matter is
0.6MPa-1.2MPa；The heat source temperature of warm is 75-85 DEG C, and temperature reaches 40 DEG C -60 DEG C after the pre-heat treatment；After pressure stabilizing
Ammonia pressure be 0.6MPa-1.2MPa；
3) ammonia after pressure stabilizing in step 2) is passed through first reactor, occurred under stiring with the propionic acid in first reactor anti-
It answers；
4) the cooling first reactor and second reactor, control 110 DEG C -130 DEG C of reaction temperature, and carry out pressure stabilizing again,
Ammonia pressure is 0.6MPa-1.2MPa after pressure stabilizing；
5) after pressure stabilizing, more than the ammonia and propionic acid sustained response 1h in first reactor, then make the ammonia in first reactor
Be spilled over to second reactor, reacted with the propionic acid in second reactor, while opening third reactor, and to third reactor into
Row cools；
6) after the ammonia in first reactor and propionic acid the reaction was continued 2-2.5h, ammonia is made in second reactor to be spilled over to third anti-
Device is answered, is reacted with the propionic acid in third reactor, and measures the content of propionic acid ammonium in propionic acid liquid in third reactor；
7) when the content for detecting propionic acid ammonium in propionic acid liquid accounts for propionic acid liquid and propionic acid ammonium mixture quality in third reactor
When 10%-15%, stopping is passed through ammonia, continues after stirring a period of time, by the first reactor and the second reactor
Middle spilling has neither part nor lot in reaction and remaining ammonia leads in fresh propionic acid solution and carries out other batch productions；
8) product in first reactor is taken out, cooling obtains propionic acid ammonium crystal；
9) reaction solution in second reactor is replaced in the first reactor, carries out the preparation of lower batch propionic acid ammonium；By
Propionic acid liquid in three reactors takes out, and storage is used for the preparation of other batch propionic acid ammoniums.
2. the preparation method of propionic acid ammonium crystal according to claim 1, which is characterized in that in the step 1), stirring
Mixing speed is 45r/min-50r/min.
3. the preparation method of propionic acid ammonium crystal according to claim 2, which is characterized in that the first reaction in the step 1)
Propionic acid additional amount is every 1m in device3Middle addition 600kg-700kg；Propionic acid additional amount in the second reactor and third reactor
For every 1m3Middle addition 700kg-800kg.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5082675A (en) * | 1989-07-29 | 1992-01-21 | Bp Chemicals Limited | Ensiling composition |
| CN1961720A (en) * | 2006-11-30 | 2007-05-16 | 上海交通大学 | Mold-proof oxidation-resistant compound additive |
| CN101731451A (en) * | 2010-01-21 | 2010-06-16 | 鲁昊 | Compound mouldproof agent with acidizing effect and preparation method thereof |
| CN102919551A (en) * | 2012-11-22 | 2013-02-13 | 生物源生物技术（深圳）有限公司 | Method for producing propionic acid type mildewproof agent by utilizing microbial fermentation method, and application thereof |
| CN202823327U (en) * | 2012-08-31 | 2013-03-27 | 南京扬子精细化工有限责任公司 | Gas liquid reaction device suitable for ammonium propionate solution |
-
2015
- 2015-11-12 CN CN201510770377.XA patent/CN106699544B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5082675A (en) * | 1989-07-29 | 1992-01-21 | Bp Chemicals Limited | Ensiling composition |
| CN1961720A (en) * | 2006-11-30 | 2007-05-16 | 上海交通大学 | Mold-proof oxidation-resistant compound additive |
| CN101731451A (en) * | 2010-01-21 | 2010-06-16 | 鲁昊 | Compound mouldproof agent with acidizing effect and preparation method thereof |
| CN202823327U (en) * | 2012-08-31 | 2013-03-27 | 南京扬子精细化工有限责任公司 | Gas liquid reaction device suitable for ammonium propionate solution |
| CN102919551A (en) * | 2012-11-22 | 2013-02-13 | 生物源生物技术（深圳）有限公司 | Method for producing propionic acid type mildewproof agent by utilizing microbial fermentation method, and application thereof |
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