CN102040400B - Green synthesis process of slow release carbon base nitrogen fertilizer - Google Patents
Green synthesis process of slow release carbon base nitrogen fertilizer Download PDFInfo
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- CN102040400B CN102040400B CN201010551219A CN201010551219A CN102040400B CN 102040400 B CN102040400 B CN 102040400B CN 201010551219 A CN201010551219 A CN 201010551219A CN 201010551219 A CN201010551219 A CN 201010551219A CN 102040400 B CN102040400 B CN 102040400B
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- 0 C*(C)C(*N)=* Chemical compound C*(C)C(*N)=* 0.000 description 2
- ZLUHSZYPJUQVMJ-UHFFFAOYSA-N [NH-][NH+](C1OC1NN)N Chemical compound [NH-][NH+](C1OC1NN)N ZLUHSZYPJUQVMJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for synthesizing polycarboureide and relates to the synthesis of a urea condensation polymer, solving the problems that in the traditional preparation method of the urea condensation polymers, used raw materials have damage to the human body and the environment and low productivity and generate side products having damages to the human body and the environment. The method disclosed by the invention comprises the following steps of: heating dipropyl carbonate up to 40-50 DEG C in a reactor; then respectively adding urea and a catalyst; heating up to a temperature above the melting point of the urea and heating for 5-10 hours; then cooling to room temperature while stirring; filtering to recover liquid-phase normal propyl alcohol, and washing an obtained solid phase to remove normal propyl alcohol and dipropyl carbonate attached to the surface of the solid phase; and then drying at 90-100 DEG C to obtain the polycarboureide. The method is a green synthesis process, cannot generate side products having damages to the human body and can be used for flexibly controlling the polymerization degree of the generated polycarboureide.
Description
Technical field
The present invention relates to the synthetic of a kind of urea polycondensate, be specially the synthetic method of the poly-carbonyl urea of a kind of slowly-releasing carbon back nitrogenous fertilizer.
Background technology
The study on the synthesis of urea polycondensate starts from the synthetic of biuret the earliest, up to now, the synthetic method of biuret mainly contains three kinds, wherein two kinds of methods are to utilize cyanic acid or ammonium cyanate and urea reaction to prepare biuret, another kind method is to more than the fusing point with the urea direct heating, perhaps in inert solvent, urea is heated to more than the fusing point, part urea generation decomposition reaction this moment loses ammonia and generates cyanic acid, condensation reaction further takes place in the cyanic acid and the undecomposed urea that generate, finally generates biuret.
When practical application, there is following defective in these three kinds of methods: preceding two kinds of production costs are higher, and cyanic acid and ammonium cyanate all be highly toxic product, itself prepare also serious environment pollution, are not suitable for large-scale industrial production; The third method has a large amount of ammonias to emit when generating biuret, has consumed the nitrogen element of preciousness in the urea molecule, and industrial efficiency and social benefit are all lower.At present, be based upon that the preparation method through improved biuret mainly contains on the third method basis:
(1) inert solvent method.This method is that the pyrolytic reaction of urea is carried out in inert solvent, and inert solvent commonly used is bis ether compounds such as diethylene glycol dimethyl ether, dibutyl ethylene glycol ether.This method is convenient to the temperature of strict control pyrolytic reaction, thereby makes the by product cyanuric acid and the growing amount of the triuret that contracts drops to minimumly, helps the release of ammonia simultaneously, has promoted molecular balance to move to the product direction, and product separating technique is also fairly simple.
(2) negative pressure method.This method normally prepares in the process of biuret decompression so that remove by product ammonia in the urea melting polymerization, thereby molecular balance is moved to the product direction, improves the productive rate of biuret.
(3) catalyzing and condensing method.This method is to add catalyzer on urea direct melting copolymerization method or inert solvent method and decompression method basis.Catalyzer commonly used has tosic acid, the oxide compound of Mo, P, B and NH
4MoO
4, HBO
3Deng.
Above-mentioned the whole bag of tricks productive rate generally is all lower, and yield is generally 30%～38%, and negative pressure method productive rate is the highest, but also can only reach 50%.In above-mentioned three kinds of methods: also can take reactants such as part urea when the negative pressure method is being taken out deammoniation gas out of, thereby stop up vacuum pipe; The catalyzing and condensing method is also relatively more difficult in the separation of catalyzer; There is the problem of solvent recuperation in the inert solvent method when producing, make production technique become complicated.
Nineteen forty-three, it is the route of the synthetic triuret that contracts of raw material that the Hoechst of Germany has reported with the urea photoreactive gas, and reaction equation is as follows:
The preparation method of many ureas of contracting sees the report of Berlin, Germany Free University (Freien Universit t Berlin) Fu Lanke ﹒ borna (Frank B rner) Ph D dissertation in 1999 the earliest.The first step of this method is to make cyanuric chloride generation pyrolysis generate carbonic acid vulcabond and chlorine, second step was to generate five ureas that contract with urea reaction again by the carbonic acid vulcabond, reaction generates contract five ureas also can be further and carbonic acid vulcabond and urea reaction, generate contract nine ureas or the higher many ureas that contract of the polymerization degree.The advantage of this method is not produce ammonia in the reaction, and shortcoming is to have a large amount of chlorine to generate corrosive equipment and contaminate environment after the cyanuric chloride thermolysis.
The contriver thinks that in fact many ureas that contract can be regarded as with carbonyl and a plurality of urea molecules are coupled together and the poly-carbonyl urea that forms, produced thus with the ammonolysis reaction of the carbonyl in the carbonic ether molecule by ester, urea molecule is coupled together the conception of the poly-carbonyl urea of preparation, so that a kind of green synthesis process of slowly-releasing carbon back nitrogenous fertilizer to be provided.
Summary of the invention
The present invention is that productive rate is low, and can generate the problem to human body and the deleterious by product of environment, and a kind of synthetic method of poly-phosphinylidyne urea is provided for the raw material of the use of the preparation method's existence that solves the existing urea polycondensate is harmful to human body and environment.
The present invention uses nontoxic dipropyl carbonate and urea by the ammonolysis reaction of ester, with the carbonyl in the dipropyl carbonate molecule (carbonic acyl radical) urea molecule is coupled together, and has synthesized the poly-carbonyl urea of polymerization degree n=1～5.Its by product n-propyl alcohol also is nontoxic, and can be converted into dipropyl carbonate again with carbon dioxide reaction under the katalysis of cerium oxide, thereby realizes the recycle of n-propyl alcohol.The present invention comes down to have fixed gaseous carbon dioxide with urea, and generally acknowledged greenhouse gases carbonic acid gas is transformed into can be by the carbon back fertilizer of plant absorbing, thereby reaches the purpose of development low-carbon (LC) agricultural.
The present invention is achieved by the following technical solutions:
With dipropyl carbonate heat temperature raising to 40～50 ℃ in reactor, add urea and catalyzer then respectively, be warming up to the above temperature of urea fusing point again, heating 5～10h under agitation is cooled to room temperature then, the n-propyl alcohol of filtered and recycled liquid phase, solid phase attaches at its surperficial n-propyl alcohol and dipropyl carbonate to remove with washing with alcohol, in 90～100 ℃ of dryings, must gather the carbonyl urea then, be slowly-releasing carbon back nitrogenous fertilizer, its reaction formula is as follows:
In the formula: n=1～5.
Described urea is the dry small particle urea that particle diameter is not more than 2mm.
Described dipropyl carbonate is a technical grade.
The mol ratio of described dipropyl carbonate and urea is 1:1～2.
Described catalyzer can be any one or any several mixtures with arbitrary proportion of yellow soda ash, salt of wormwood, sodium methylate, potassium methylate, sodium formiate, potassium formiate, sodium oxalate or potassium oxalate.
Described catalyst consumption is 0.5%～2.5% of a dipropyl carbonate quality.
Described when being warming up to the above temperature of urea fusing point, top temperature is not higher than 160 ℃.
Compared with prior art, the present invention has following beneficial effect:
(1) with carbonyl with urea molecule couple together change poly-carbonyl urea into after, can give urea with certain slow-releasing, by regulating the mean polymerisation degree n value of poly-carbonyl urea, can regulate nitrogen element rate of release flexibly, the urea of instantly-soluble can be changed into the controlled chemotype slow-release carbamide of nitrogen element rate of release, to improve the effective rate of utilization of urea.
(2) dipropyl carbonate is nontoxic, compares with phosgenation or cyanuric chloride method, replaces phosgene or carbonic acid vulcabond as acylating agent with dipropyl carbonate, can avoid using the raw material (phosgene) or the bigger raw material (cyanuric chloride) of toxicity of severe toxicity.
(3) this synthesis technique unique side product n-propyl alcohol is nontoxic, and comparing with phosgenation not can mordant hydrogen chloride gas association; Comparing with the cyanuric chloride method can toxic very high chlorine association.
(4) n-propyl alcohol is under the katalysis of cerium oxide, can with carbon dioxide reaction, be converted into dipropyl carbonate, thereby realize the recycle of n-propyl alcohol.
(5) this synthesis technique is equivalent in fact fix gaseous carbon dioxide with urea, has been transformed into the poly-carbonyl urea of carbon containing, hydrogen, oxygen, four kinds of nutritive elements of nitrogen, and the greenhouse gases carbonic acid gas is turned waste into wealth.
Description of drawings
Fig. 1 is a process flow sheet of the present invention;
Fig. 2 is 1 poly-carbonyl urea for polymerization degree n
1The H-NMR spectrogram;
Fig. 3 is 2 poly-carbonyl urea for polymerization degree n
1The H-NMR spectrogram;
Fig. 4 is 4 poly-carbonyl urea for polymerization degree n
1The H-NMR spectrogram;
Fig. 5 is 5 poly-carbonyl urea for polymerization degree n
1The H-NMR spectrogram.
Embodiment
Embodiment 1: mean polymerisation degree n is 1 poly-carbonyl urea
Mean polymerisation degree n is 1 poly-carbonyl urea, and its molecular structural formula is as follows:
This poly-carbonyl urea can regard 2 urea molecules as and 1 dipropyl carbonate molecule is eliminated the product (being equivalent to the triuret that contracts) that 2 molecule n-propyl alcohol polycondensations form by the ammonolysis reaction of ester, and the massfraction of nitrogen element is 38.35%, and its preparation method is as follows:
Mol ratio by n (dipropyl carbonate): n (urea)=1:2 takes by weighing raw material, the urea particle diameter is 1.3mm, dipropyl carbonate is a technical grade, catalyzer is selected yellow soda ash (also can be sodium methylate, potassium methylate, salt of wormwood, sodium formiate, potassium formiate, sodium oxalate or potassium oxalate) for use, and quality is 2.5% of a dipropyl carbonate quality.At first dipropyl carbonate is joined in the reactor, during heat temperature raising to 40 ℃, under mechanical stirring, add the urea of having dried in batches, urea adds the back that finishes and adds catalyzer, is heated to 150～160 ℃, and picks up counting, stop heating behind the reaction 5h, under brute force stirs, be cooled to room temperature, filter, after solid-liquid two is separated, reclaim the n-propyl alcohol of liquid phase, solid phase is washed with adequate amount of ethanol, removes to attach at its surperficial n-propyl alcohol and dipropyl carbonate, then in 90～100 ℃ of dryings.The reaction products therefrom passes through
1The H-NMR spectrogram is measured and is confirmed that mean polymerisation degree n is 1, as shown in Figure 2.
Embodiment 2: mean polymerisation degree n is 2 poly-carbonyl urea
Mean polymerisation degree n is 2 poly-carbonyl urea, and its molecular structural formula is as follows:
This poly-carbonyl urea can regard 3 urea molecules as and 2 dipropyl carbonate molecules are eliminated the product (five ureas are equivalent to contract) that 4 molecule n-propyl alcohol polycondensations form by the ammonolysis reaction of ester, and the massfraction of nitrogen element is 36.20%, and its preparation method is as follows:
Mol ratio by n (dipropyl carbonate): n (urea)=1:1.5 takes by weighing raw material, and the urea particle diameter is 1.5mm, and dipropyl carbonate is a technical grade, and catalyzer is selected Anhydrous potassium carbonate for use, and quality is 2.0% of a dipropyl carbonate quality.At first dipropyl carbonate is joined in the reactor, during heat temperature raising to 45 ℃, under mechanical stirring, add the urea of having dried in batches, urea adds the back that finishes and adds catalyzer, is heated to 145～155 ℃, and picks up counting, stop heating behind the reaction 6h, under brute force stirs, be cooled to room temperature, filter, after solid-liquid two is separated, reclaim the n-propyl alcohol of liquid phase, solid phase is washed with adequate amount of ethanol, removes to attach at its surperficial n-propyl alcohol and dipropyl carbonate, then in 90～100 ℃ of dryings.The reaction products therefrom passes through
1The H-NMR spectrogram is measured and is confirmed that mean polymerisation degree n is 2, as shown in Figure 3.
Embodiment 3: mean polymerisation degree n is 4 poly-carbonyl urea
Mean polymerisation degree n is 4 poly-carbonyl urea, and its molecular structural formula is as follows:
Should can regard 5 urea molecules and 4 products (nine ureas are equivalent to contract) that the dipropyl carbonate molecule is polymerized by eliminating 8 molecule propyl alcohol as by poly-carbonyl urea, the massfraction of nitrogen element is 34.65%, and its preparation method is as follows:
Mol ratio by n (dipropyl carbonate): n (urea)=1:1.25 takes by weighing raw material, the urea particle diameter is 1.8mm, dipropyl carbonate is a technical grade, and it is 2:1:1 potassium methylate, salt of wormwood and yellow soda ash that catalyzer is selected mol ratio for use, and quality is 1.0% of a dipropyl carbonate quality.At first dipropyl carbonate is joined in the reactor, during heat temperature raising to 50 ℃, under mechanical stirring, add the urea of having dried in batches, urea adds the back that finishes and adds catalyzer, is heated to 133～140 ℃, and picks up counting, stop heating behind the reaction 8h, under brute force stirs, be cooled to room temperature, filter, after solid-liquid two is separated, reclaim the n-propyl alcohol of liquid phase, solid phase is washed with adequate amount of ethanol, removes to attach at its surperficial n-propyl alcohol and dipropyl carbonate, then in 90～100 ℃ of dryings.The reaction products therefrom passes through
1The H-NMR spectrogram is measured and is confirmed that n is 4, as shown in Figure 4.
Embodiment 4: mean polymerisation degree n is 5 poly-carbonyl urea
Mean polymerisation degree n is 5 poly-carbonyl urea, and its molecular structural formula is as follows:
Should can regard 6 urea molecules and 5 products (11 ureas are equivalent to contract) that the dipropyl carbonate molecule is polymerized by eliminating 10 molecule propyl alcohol as by poly-carbonyl urea, the massfraction of nitrogen element is 34.29%, and its preparation method is as follows:
Mol ratio by n (dipropyl carbonate): n (urea)=1:1.2 takes by weighing raw material, and the urea particle diameter is 2mm, and dipropyl carbonate is a technical grade, and catalyzer such as selects for use at the potassium formiate of mol ratio and the mixture of potassium oxalate, and total mass is 0.5% of a dipropyl carbonate quality.At first dipropyl carbonate is joined in the reactor, during heat temperature raising to 47 ℃, under mechanical stirring, add the urea of having dried in batches, urea adds the back that finishes and adds catalyzer, is heated to 140～150 ℃, and picks up counting, stop heating behind the reaction 10h, under brute force stirs, be cooled to room temperature, filter, after solid-liquid two is separated, reclaim the n-propyl alcohol of liquid phase, solid phase is washed with adequate amount of ethanol, removes to attach at its surperficial n-propyl alcohol and dipropyl carbonate, then in 90～100 ℃ of dryings.The reaction products therefrom passes through
1The H-NMR spectrogram is measured and is confirmed that mean polymerisation degree n is 5, as shown in Figure 5.
Claims (3)
1. the green synthesis method of a slowly-releasing carbon back nitrogenous fertilizer, it is characterized in that: with dipropyl carbonate heat temperature raising to 40～50 ℃ in reactor, add urea and catalyzer then respectively, the mol ratio of wherein said dipropyl carbonate and urea is 1:1～2, catalyst consumption is 0.5%～2.5% of a dipropyl carbonate quality, described catalyzer is a yellow soda ash, salt of wormwood, sodium methylate, potassium methylate, sodium formiate, potassium formiate, sodium oxalate, or any one or any several mixtures of potassium oxalate with arbitrary proportion, be warming up to the above temperature of urea fusing point again, and top temperature is not higher than 160 ℃, heating 5～10h, under agitation be cooled to room temperature then, the n-propyl alcohol of filtered and recycled liquid phase, solid phase attaches at its surperficial n-propyl alcohol and dipropyl carbonate to remove with washing with alcohol, then in 90～100 ℃ of dryings, must gather the carbonyl urea, be slowly-releasing carbon back nitrogenous fertilizer, its composition principle is as follows:
In the formula: n=1～5.
2. according to the green synthesis method of the described a kind of slowly-releasing carbon back nitrogenous fertilizer of claim 1, it is characterized in that described urea is the dry small particle urea that particle diameter is not more than 2mm.
3. according to the green synthesis method of claim 1 or 2 described a kind of slowly-releasing carbon back nitrogenous fertilizer, it is characterized in that described dipropyl carbonate is a technical grade.
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| CN102584458B (en) * | 2012-02-29 | 2013-08-07 | 中北大学 | Multiple nutrient macromolecule slow release carbon-base fertilizer and preparation method thereof |
| CN104446675B (en) * | 2014-11-10 | 2016-11-09 | 成都新柯力化工科技有限公司 | A kind of high molecular polymer slow-release nitrogen fertilizer and preparation method thereof |
| CN104478620A (en) * | 2014-12-31 | 2015-04-01 | 吴中区金庭小美华家庭农场 | Acetal-containing vegetable leaf fertilizer and preparation method thereof |
| CN106916302A (en) * | 2015-12-25 | 2017-07-04 | 广州亿奇科技股份有限公司 | modified urea product, preparation method and its application in transparent soap |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3712879A (en) * | 1969-04-05 | 1973-01-23 | G Blume | Urea formaldehyde condensation products |
| CN1990428A (en) * | 2005-12-26 | 2007-07-04 | 曹承绵 | Urea methanal preparing technique |
| CN101353270A (en) * | 2008-09-08 | 2009-01-28 | 中国海洋石油总公司 | Preparation of low aldehyde long-acting urea-formaldehyde slow release fertilizer |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3712879A (en) * | 1969-04-05 | 1973-01-23 | G Blume | Urea formaldehyde condensation products |
| CN1990428A (en) * | 2005-12-26 | 2007-07-04 | 曹承绵 | Urea methanal preparing technique |
| CN101353270A (en) * | 2008-09-08 | 2009-01-28 | 中国海洋石油总公司 | Preparation of low aldehyde long-acting urea-formaldehyde slow release fertilizer |
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