CN102633736A - Method for synthesizing cyanic acid or melamine by utilizing ammonia gas and carbon dioxide - Google Patents

Method for synthesizing cyanic acid or melamine by utilizing ammonia gas and carbon dioxide Download PDF

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CN102633736A
CN102633736A CN2012100997478A CN201210099747A CN102633736A CN 102633736 A CN102633736 A CN 102633736A CN 2012100997478 A CN2012100997478 A CN 2012100997478A CN 201210099747 A CN201210099747 A CN 201210099747A CN 102633736 A CN102633736 A CN 102633736A
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ammonia
trimeric cyanamide
reaction
acid
tricyanic
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CN102633736B (en
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朱维群
王倩
阿不都拉江·那斯尔
宋名秀
孙洪志
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Shandong University
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Abstract

The invention relates to a method for synthesizing cyanic acid or melamine by utilizing ammonia gas and carbon dioxide. The method comprises the following steps: directly reacting by taking ammonia gas and carbon dioxide as raw materials or taking ammonium bicarbonate, ammonium carbonate and ammonium carbamate as the raw materials in the presence of a catalyst or no catalyst under the conditions that the temperature is 200-300 DEG C and the pressure is 0-30MPa to obtain a cyanic acid or melamine product. By using the method disclosed by the invention, a series of problems during the synthesis process of urea are avoided, synthesis production cycle energy consumption, consumption of manpower and physical resources of cyanic acid or melamine are reduced, and production cost is lowered.

Description

Utilize the method for synthetic tricyanic acid of ammonia and carbonic acid gas or trimeric cyanamide
Technical field
The present invention relates to a kind of tricyanic acid and trimeric cyanamide synthetic method, belong to chemical technology field.
Technical background
Tricyanic acid and trimeric cyanamide all belong to the triazines heterogeneous ring compound, all are the more important Chemicals of China recent years development.The structural formula of tricyanic acid (a) and trimeric cyanamide (b) is following:
Figure BDA0000150995260000011
Tricyanic acid has another name called cyamelide or cyanuric acid, is a kind of broad-spectrum synthetic intermediate, and like synthetic resins, fire retardant, weedicide etc., tricyanic acid relates to fields such as medicine, agricultural chemicals, coating, weaving, light industry as the raw material of synthetic resins.The synthesis route of tricyanic acid generally has following several kinds:
1 phosgene and ammonia react:
6COCl 2+6NH 3→2C 3N 3H 3O 3+12HCl
2 cyanic acid trimerizations:
3HOCN?→C 3N 3H 3O 3
3 prussic acid oxidations:
6HCN+3O 2→2C 3N 3H 3O 3
4 cyanuryl chloride hydrolysis:
C 3N 3H 3Cl 3+3H 2O→C 3N 3H 3O 3+3HCl
5 urea pyrolysis:
3CO(NH 2) 2→C 3N 3H 3O 3+3NH 3
Above-mentioned synthesis route preceding four kinds have respectively that material toxicity is big, complex process or the high shortcoming of cost, be difficult to realize large-scale industrial production.The working method of tricyanic acid generally all is to be that raw material comes synthetic (route 5) with urea at present.
Trimeric cyanamide is as the raw material of production of melamine formaldehyde resin; With urea-formaldehyde resin (UF), resol (PF) and be called three summer woods and stick with glue agent; Can also synthetic cross-linking agent, finishing composition, laking agent, flocculation agent etc., extensively apply to industries such as timber, plastics, coating, papermaking, weaving, leather, electric and medicine.
Production of Cyanuramide all is to be raw material with urea at present, makes catalyzer with aluminum oxide, silica gel, alumino silica gel etc., under 380-450 ℃ of temperature, under high pressure, low pressure or condition of normal pressure, carry out.
Chinese patent file CN102295615A (CN201110196920.1) provides a kind of method of low temperature production of melamine; Comprise that with urea condensates such as urea, biuret or tricyanic acids be raw material, 150-300 ℃, feed ammonia and keep the ammonia branch to be pressed in 0-50MPa, add catalyzer or do not add that direct reaction obtains trimeric cyanamide under the catalyzer condition.When adding catalyzer, preferred catalyzer is ammonium chloride or ammonium sulfate, and said catalyst consumption is the 1-5wt% of raw materials quality.In the process of production of melamine, do not emit ammonia and CO 2, make raw material consumption greatly reduce, and temperature of reaction being low, thereby making simplified equipment, energy consumption reduces, and pollutes and reduces.The present invention is the further improvement on this patented claim basis of applicant.
Summary of the invention
For solving the many practical problemss that exist in prior art tricyanic acid, the Melamine Production process; Reduce tricyanic acid, Production of Cyanuramide cost; The present invention proposes the compound method of a kind of tricyanic acid, trimeric cyanamide; Be synthetic tricyanic acid of raw material or trimeric cyanamide directly, simplify operational path, reduce cost with ammonia and carbonic acid gas.
Technical scheme of the present invention is following:
The compound method of a kind of tricyanic acid, trimeric cyanamide; It is characterized in that mainly being is raw material with ammonia and carbonic acid gas; Or be raw material with bicarbonate of ammonia, volatile salt or ammonium carbamate; In temperature 200-300 ℃, pressure 0-30MPa, add catalyzer or do not add under the catalyzer condition and react, directly synthetic tricyanic acid or the trimeric cyanamide product of making;
In the mole number of ammonia and carbonic acid gas, raw materials used in ammonia: carbon dioxide reaction mol ratio=(0.5-1.2): 1 o'clock, react tricyanic acid;
In the mole number of ammonia and carbonic acid gas, raw materials used in ammonia: carbon dioxide reaction mol ratio=(2.0-4.5): 1 o'clock, react trimeric cyanamide;
When being raw material, maybe need add ammonia or carbonic acid gas, to satisfy the mol ratio of above-mentioned ammonia and carbonic acid gas with bicarbonate of ammonia, volatile salt or ammonium carbamate.
According to the present invention, bicarbonate of ammonia can directly be used for the synthetic of tricyanic acid; Through the extra ammonia of adding, make ammonia in the reaction system: the carbon dioxide reaction mol ratio=(2.0-4.5): can obtain the trimeric cyanamide product at 1 o'clock.
According to the present invention, volatile salt, ammonium carbamate can directly be used for the synthetic of trimeric cyanamide; Through extra supplementary carbon dioxide, make ammonia in the reaction system: the carbon dioxide reaction mol ratio=(0.5-1.2):, can obtain the tricyanic acid product at 1 o'clock.
According to the present invention, when adding catalyzer, preferred catalyzer is ammonium chloride or ammonium sulfate.Said catalyst consumption is the 1-5wt% of raw materials quality.The interpolation of catalyzer can be shortened the reaction times and improve reaction product content.
According to the present invention, preferred, when not adding catalyzer, at 200-300 ℃, pressure is 1-30MPa, reaction 10-60min.Most preferred, when not adding catalyzer, at 230-250 ℃, pressure is 20MPa, reaction 10-40min.
According to the present invention, preferred, when adding catalyzer, at 220-270 ℃, the maintenance reaction pressure is 5-25MPa, adds ammonium chloride or the ammonium sulfate catalyzer of the 1-5wt% that accounts for raw materials quality, reaction 1-30min.Most preferred, when adding catalyzer, 200-210 ℃, during reaction pressure 10-20MPa, reaction 10-20min.
According to the present invention, preferred, with the tricyanic acid bullion that reaction obtains, with 20% aqueous sulfuric acid purifying, cleansing temp 80-100 ℃, drying obtains the pure article of white solid tricyanic acid, content >=98wt%.
According to the present invention, preferred, with the crude product of melamine that reaction obtains, with 40-80 ℃ pure water washing, filtration 1-2 time, drying obtains the pure article of white solid trimeric cyanamide, content >=98wt%.Most preferred, with 60-80 ℃ of pure water purifying.
According to the present invention, be concrete preferred version with embodiment 1,3,4,7 with ammonia, when carbonic acid gas is raw material.
According to the present invention, be concrete preferred version with embodiment 2,5,6 with bicarbonate of ammonia, volatile salt, when ammonium carbamate is raw material.
Synthesizing on reaction mechanism of tricyanic acid of the present invention; No longer carry out the process of urea condensation generation tricyanic acid; But be raw material through ammonia and carbonic acid gas, or the reactant of ammonia and carbonic acid gas such as bicarbonate of ammonia etc. are raw material, direct reaction obtains tricyanic acid under HTHP.Synthesizing on reaction mechanism of trimeric cyanamide of the present invention; The cyanic acid that no longer carries out under the high temperature resolves into cyanamide and carbon dioxide reaction; But be raw material through ammonia and carbonic acid gas; Or the reactant of ammonia and carbonic acid gas such as volatile salt or ammonium carbamate, direct reaction obtains trimeric cyanamide under HTHP.Through different ammonia carbon ratio in the control reaction system, make tricyanic acid or trimeric cyanamide respectively.
The inventive method has changed through ammonia and carbonic acid gas elder generation urea synthesis; The process of resynthesis tricyanic acid or trimeric cyanamide; The novel method of a kind of directly synthetic tricyanic acid or trimeric cyanamide has been proposed; Different proportionings through reaction raw materials; Under certain temperature and pressure, add catalyzer or do not add under the condition of catalyzer and directly obtain tricyanic acid or trimeric cyanamide, having avoided with ammonia and carbonic acid gas is the problem that must adopt the strict control of certain technical measures by product biuret to produce in the raw material urea synthesis process; Simultaneously, having significantly reduced production cycle, energy consumption and the human and material resources consumption of being synthesized title product by two step processes in the past, reduced production cost, is the green production method of a kind of tricyanic acid or trimeric cyanamide; In addition, in the inventive method synthetic still a kind of reasonable collecting carbonic anhydride of tricyanic acid with seal technology up for safekeeping, can carbonic acid gas be converted into important chemical product tricyanic acid, have important use and be worth.
The process of synthetic tricyanic acid or trimeric cyanamide is gas-solid phase or heterogeneous reaction in the inventive method, and its speed of response is relevant with the dosage of heating rate and catalyzer.Because reaction product exists with solid-state form, therefore can obtain highly purified product through simple purifying in reaction system.According to the present invention, the content of reacted tricyanic acid or trimeric cyanamide >=95%, productive rate >=95%, tricyanic acid behind the purifying or the content of trimeric cyanamide >=98%, productive rate >=95%.
The present invention is unexpected to be found in industrial production directly to be reacted under HTHP by ammonia and carbonic acid gas and obtains tricyanic acid and trimeric cyanamide has more meliority; This production process is that raw material can reduce production costs than with urea; Particularly by ammonia and the directly synthetic tricyanic acid of carbon dioxide reaction; Having avoided existing urea is the invalid circulation of ammonia in the raw material synthesis technique; Practicing thrift the mass production cost, is the green synthetic route of a tricyanic acid, also is a kind of simple more directly process method that is suitable for suitability for industrialized production.
Embodiment
Below in conjunction with embodiment the present invention is further specified, but be not limited thereto.Below in conjunction with embodiment the present invention is further specified, but be not limited thereto.Involved percentage composition is a mass percent among the embodiment, and aqueous sulfuric acid concentration is mass percent.Wherein, embodiment 1-3 is the synthetic explanation of tricyanic acid, and embodiment 4-7 is the synthetic explanation of trimeric cyanamide.
Embodiment 1. is the synthetic tricyanic acid of raw material with ammonia, carbonic acid gas, and reaction formula is:
3CO 2+3NH 3→C 3N 3H 3O 3+3H 2O
Press n (NH 3): n (CO 2The mol ratio of)=0.8: 1 feeds ammonia 440g, carbonic acid gas 1040g in reactor drum, at 240-250 ℃, keeping system's reaction pressure is 20.0MPa, reaction 10min; Reaction product is mainly white tricyanic acid (C 3N 6H 3O 3) solid, content is 95%, and content is 98% behind the purifying, and productive rate is 95%;
Embodiment 2. is the synthetic tricyanic acid of raw material with bicarbonate of ammonia, and reaction formula is:
3NH 4HCO 3→C 3N 3H 3O 3+6H 2O
In reactor drum, add bicarbonate of ammonia 670g, at 230-250 ℃, keeping system's reaction pressure is 20.0MPa, reaction 5min; Reaction product is mainly white tricyanic acid (C 3N 6H 3O 3) solid, content is 95.2%, and content is 98.5% behind the purifying, and productive rate is 95%.
Embodiment 3. is that raw material synthesizes tricyanic acid at catalytic condition with ammonia and carbonic acid gas, and reaction formula is:
Figure BDA0000150995260000041
Press n (NH 3): n (CO 2The reacting weight of)=1.1: 1 adds ammonia 440g, carbonic acid gas 1040g and 50g ammonium chloride in reactor drum, be heated to 200-210 ℃, and keeping system's reaction pressure is 15.0MPa, reaction 15min; Reaction product is mainly white tricyanic acid (C 3N 6H 3O 3) solid, content is 96%, and content is 99% behind the purifying, and productive rate is 96%.
Embodiment 4. is the raw material production of melamine with ammonia, carbonic acid gas, and reaction formula is:
3CO 2+6NH 3→C 3N 6H 6+6H 2O
Press n (NH 3): n (CO 2The reaction mol ratio of)=2.2: 1 adds ammonia 585g, carbonic acid gas 695g in reactor drum, at 230-250 ℃, keeping system's reaction pressure is 20.0MPa, reaction 40min; Reaction product is mainly white trimeric cyanamide (C 3N 6H 6) solid, content is 95%, and content is 98% behind the purifying, and productive rate is 95%.
Embodiment 5. is the raw material production of melamine with the volatile salt, and reaction formula is:
3(NH 4) 2CO 3→C 3N 6H 6+9H 2O
In reactor drum, add volatile salt 570g, at 230-250 ℃, keeping system's reaction pressure is 20.0MPa, reaction 30min; Reaction product is mainly white trimeric cyanamide (C 3N 6H 6) solid, content is 95.5%, and content is 98.5% behind the purifying, and productive rate is 95%.
Embodiment 6. is the raw material production of melamine with the ammonium carbamate, and reaction formula is:
3NH 2COONH 4→C 3N 6H 6+6H 2O
In reactor drum, add ammonium carbamate (first ammonium) 710g, be heated to 230-240 ℃, keeping system's reaction pressure is 10.0MPa, reaction 30min; Reaction product is mainly white trimeric cyanamide (C 3N 6H 6) solid, content is 95%, and content is 98% behind the purifying, and productive rate is 96.
Embodiment 7. with ammonia and carbonic acid gas be raw material at the catalytic condition production of melamine, reaction formula is:
Press n (NH 3): n (CO 2The reacting weight of)=2.2: 1 adds ammonia 585g, carbonic acid gas 695g and 55g ammonium chloride in reactor drum, at 200-210 ℃, keeping system's reaction pressure is 15.0MPa, reaction 20min; Reaction product is mainly white trimeric cyanamide (C 3N 6H 6) solid, content is 96%, and content is 99% behind the purifying, and productive rate is 96%.
The product that the inventive method obtains be content at tricyanic acid more than 95% or trimeric cyanamide, by-products content seldom, purification process also can be in industrial production be directly used.If can carry out purifying through current purification method when needing pure article.Product tricyanic acid purification process of the present invention heats 80-100 ℃ for adopting 20% aqueous sulfuric acid, and washing and filtering purifying 1-2 time gets the pure article of tricyanic acid.The method that can carry out purifying to product trimeric cyanamide of the present invention heats 40-80 ℃ for adopting pure water, and washing and filtering purifying 1-2 time gets the pure article of trimeric cyanamide.

Claims (7)

1. the compound method of tricyanic acid or trimeric cyanamide; It is characterized in that being raw material or being raw material with bicarbonate of ammonia, volatile salt or ammonium carbamate with ammonia and carbonic acid gas; In temperature 200-300 ℃, pressure 0-30MPa, add catalyzer or do not add under the catalyzer condition and react, directly synthetic tricyanic acid or the trimeric cyanamide product of making;
In the mole number of ammonia and carbonic acid gas, raw materials used in ammonia: carbon dioxide reaction mol ratio=(0.5-1.2): 1 o'clock, react tricyanic acid;
In the mole number of ammonia and carbonic acid gas, raw materials used in ammonia: carbon dioxide reaction mol ratio=(2.0-4.5): 1 o'clock, react trimeric cyanamide;
When being raw material, maybe need add ammonia or carbonic acid gas, to satisfy the mol ratio of above-mentioned ammonia and carbonic acid gas with bicarbonate of ammonia, volatile salt or ammonium carbamate.
2. the compound method of tricyanic acid as claimed in claim 1 or trimeric cyanamide is characterized in that said catalyzer is ammonium chloride or ammonium sulfate when adding catalyzer.
3. according to claim 1 or claim 2 tricyanic acid or the compound method of trimeric cyanamide is characterized in that said catalyst consumption is the 1-5wt% of raw materials quality when adding catalyzer.
4. the compound method of tricyanic acid as claimed in claim 1 or trimeric cyanamide, when it is characterized in that not adding catalyzer, at 200-300 ℃, pressure is 10-30MPa, reaction 10-60min.
5. the compound method of tricyanic acid as claimed in claim 3 or trimeric cyanamide is characterized in that at 220-270 ℃, the maintenance reaction pressure is 5-25MPa when adding catalyzer, reaction 1-30min.
6. the compound method of tricyanic acid as claimed in claim 1 or trimeric cyanamide; The product tricyanic acid bullion that it is characterized in that reaction is obtained is with 20% aqueous sulfuric acid purifying, and cleansing temp 80-100 ℃, drying; Obtain the pure article of white solid tricyanic acid, content >=98wt%.
7. the compound method of tricyanic acid as claimed in claim 1 or trimeric cyanamide is characterized in that the product crude product of melamine that reaction is obtained washs, filters 1-2 time with 40-80 ℃ of pure water, and drying obtains the pure article of white solid trimeric cyanamide, content >=98wt%.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105829289A (en) * 2013-12-17 2016-08-03 斯塔米卡邦有限公司 Integrated production of urea and melamine
CN105949462A (en) * 2016-07-18 2016-09-21 山东大学 Synthesizing method of cyanuric acid macromolecule prepolymer
CN107964426A (en) * 2017-12-04 2018-04-27 山东大学 A kind of fossil fuel hydrogen production process of carbon dioxide zero discharge
CN108059977A (en) * 2017-12-22 2018-05-22 山东大学 A kind of near-zero release, CO2The fossil energy Application way of recycling

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Publication number Priority date Publication date Assignee Title
WO2009007813A1 (en) * 2007-07-09 2009-01-15 Eurotecnica Malamine Luxemburg, Zweigniederlassung In Ittigen Improved process for the treatment of retentate in a melamine production plant
CN102295615A (en) * 2011-07-14 2011-12-28 山东大学 Method for synthesizing melamine at low temperature

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009007813A1 (en) * 2007-07-09 2009-01-15 Eurotecnica Malamine Luxemburg, Zweigniederlassung In Ittigen Improved process for the treatment of retentate in a melamine production plant
CN102295615A (en) * 2011-07-14 2011-12-28 山东大学 Method for synthesizing melamine at low temperature

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105829289A (en) * 2013-12-17 2016-08-03 斯塔米卡邦有限公司 Integrated production of urea and melamine
CN105829289B (en) * 2013-12-17 2019-07-26 斯塔米卡邦有限公司 The integration production of urea and melamine
CN105949462A (en) * 2016-07-18 2016-09-21 山东大学 Synthesizing method of cyanuric acid macromolecule prepolymer
CN105949462B (en) * 2016-07-18 2018-11-13 山东大学 The synthetic method of cyanuric acid macromolecule performed polymer
CN107964426A (en) * 2017-12-04 2018-04-27 山东大学 A kind of fossil fuel hydrogen production process of carbon dioxide zero discharge
CN108059977A (en) * 2017-12-22 2018-05-22 山东大学 A kind of near-zero release, CO2The fossil energy Application way of recycling
CN108059977B (en) * 2017-12-22 2021-03-26 山东大学 Near zero emission and CO (carbon monoxide)2Resource utilization fossil energy utilization method

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