CN110272352B - Method for producing oxamide by utilizing ammonia synthesis-ammonium bicarbonate coproduction process - Google Patents
Method for producing oxamide by utilizing ammonia synthesis-ammonium bicarbonate coproduction process Download PDFInfo
- Publication number
- CN110272352B CN110272352B CN201910610178.0A CN201910610178A CN110272352B CN 110272352 B CN110272352 B CN 110272352B CN 201910610178 A CN201910610178 A CN 201910610178A CN 110272352 B CN110272352 B CN 110272352B
- Authority
- CN
- China
- Prior art keywords
- gas
- ammonium
- oxamide
- semi
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/26—Carbonates or bicarbonates of ammonium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for producing oxamide by utilizing a process of ammonia synthesis and ammonium bicarbonate coproduction, which is implemented according to the following steps: step 1, feeding semi-water gas into a gas holder by utilizing a process of ammonia synthesis and ammonium bicarbonate coproduction, pumping the semi-water gas in the gas holder by using a Roots blower, desulfurizing the semi-water gas, then feeding the semi-water gas into a first section and a second section of a compressor to be compressed to 0.7Mpa, cooling the semi-water gas to room temperature, canceling a conversion section, and directly removing carbon dioxide to obtain a feed gas; step 2, raising the pressure of the feed gas through a compressor three-section mode, heating the feed gas by using heat conduction oil, and then feeding the feed gas into a carbonization tower of an oxamide workshop, wherein carbon monoxide in the feed gas and ammonia water in the carbonization tower are catalyzed by sulfuric acid to prepare ammonium formate; step 3, carrying out dimerization and dehydrogenation on ammonium formate to obtain ammonium monohydrochloride, and carrying out dehydration on the ammonium monohydrochloride to obtain anhydrous ammonium oxalate; and 4, dehydrating the anhydrous ammonium oxalate to obtain the oxamide. The method has the advantages of low cost of the oxamide, no pollution in the production process and simple operation.
Description
Technical Field
The invention belongs to the technical field of oxamide production methods, and particularly relates to a method for producing oxamide by using a synthetic ammonia-ammonium bicarbonate coproduction process.
Background
Oxamides are also known as oxalyldiamide, oxalamides. The molecular formula is as follows: (CONH)2)2The nitrogen-containing organic silicon dioxide film contains 31.81% of nitrogen, is white crystals, is slightly soluble in hot water and ethanol, is almost insoluble in cold water, has the solubility of 0.04 g at 7 ℃, the solubility of 0.6 g at 100 ℃, the melting point of 419 ℃, the specific gravity of 1.667, does not absorb water, is non-toxic, and can be stored for an indefinite period.
Agricultural practices prove that oxamide is an excellent slow-release nitrogen fertilizer, and among a plurality of slow/controlled release fertilizers, oxamide ((CONH)2)2) The fertilizer has wider development and application prospects, can meet the requirement of crops on nitrogen in the whole growth period, reduce the loss caused by leaching loss, volatilization and denitrification of the nitrogen, improve the utilization rate of the fertilizer, reduce the fertilization times, and save labor and time; meanwhile, the carbon-nitrogen ratio of the oxamide to the ammonium bicarbonate is the same, so that the oxamide can provide proper carbon-nitrogen ratio for plants, meet the carbon-based nutritional requirements of crops, maintain the ecological balance of soil, and have been proved in regions such as Japan as the application value of high-quality slow-release fertilizer in agriculture. As early as seventies, the Japanese institute of agricultural and technology developed the fertilization of rice and wheat with oxamide synthesized with hydrocyanic acid, and the results of the fertilization varied with respect to the amount of harvested crops, the number of stalks and the number of ears of the crops The chemical and effective stalk percentage, the nitrogen content of the harvest and the like were measured in a comprehensive manner and compared, and the advantages of the oxamide nitrogen fertilizer were positively evaluated. The German Hoechst (Hoechst) company also carries out experiments at the same time, proves that the oxamide can stably provide nutrients suitable for the crops in the whole growth period of the crops, and is certainly an excellent slow-acting nitrogen fertilizer, and the fertilizer utilization rate is higher, so the oxamide is expected to be the best product for replacing urea.
The existing preparation processes of oxamide mainly comprise the following three processes:
(1) the preparation method takes hydrocyanic acid (HCN) as raw material, and the HCN is firstly oxidized to generate cyanogen ((CN): and then is hydrolyzed to prepare the oxamide. The process can be divided into Degussa process, phase model process, Asahi chemical process and Hoechat process, and the four processes are different in oxidant, catalyst and process, but all use hydrocyanic acid (HCN) as raw material, and are too high in cost. It has been reported that if the by-product from the production of acrylonitrile is used as a raw material, the process may be economically feasible, but has not been industrialized so far. The method has the defects of high toxicity and high cost of hydrocyanic acid, and no industrial report is found;
(2) pyrolysis, i.e. pyrolysis with ammonium oxalate or urea oxalate, also gives some oxamides, but this process is costly, of no practical value and involves relatively few studies.
(3) The oxalic acid diester ammonolysis method is that carbon monoxide is oxidized and coupled to synthesize oxalic acid diester, oxalic acid diester reacts with ammonia at normal pressure and normal temperature to generate oxamide, the conversion rate can reach above 98%, the generated oxamide is centrifugally dewatered, washed and dried to obtain the finished product oxamide, the purity can reach the chemical purity standard, the yield can reach above 97%, the method can synthesize oxamide by using carbon monoxide, ammonia and oxygen, and the method has great superiority from the raw material aspect. In the two-step reaction, the key is the synthesis of oxalic acid diester at the first step, although the research on the use of oxamide as a slow release fertilizer is reported abroad, the problem of large-scale commercial supply of key raw material dimethyl oxalate required by low-cost production of oxamide cannot be solved, and the report of large-scale industrial production of oxamide is not found yet.
The three processes all have too high cost to realize industrialized large-scale production, so the development and research of low-cost production of oxamide can be a great contribution to agricultural production in China, and the method has great significance for promoting the rapid development of industrial and agricultural in China and protecting the benefit of agricultural ecological environment.
Disclosure of Invention
The invention aims to provide a method for producing oxamide by utilizing a synthetic ammonia-ammonium bicarbonate coproduction process, which solves the problem of high production cost of the conventional oxamide.
The technical scheme adopted by the invention is that the method for producing oxamide by utilizing the process of ammonia synthesis and ammonium bicarbonate coproduction is implemented according to the following steps:
step 1, feeding semi-water gas produced in a gas making workshop into a gas holder by utilizing a synthetic ammonia-ammonium bicarbonate coproduction process, pumping the semi-water gas in the gas holder by using a Roots blower, desulfurizing the semi-water gas, then feeding the semi-water gas into a first section and a second section of a compressor to be compressed to 0.7Mpa, cooling the semi-water gas to room temperature, canceling a conversion section, and directly feeding the semi-water gas into a carbonization workshop to remove carbon dioxide to obtain feed gas;
step 2, the pressure of the raw material gas obtained in the step 1 is increased through a compressor in three sections, the raw material gas with the increased pressure is heated by using heat conduction oil and then enters a carbonization tower of an oxamide workshop, and carbon monoxide in the raw material gas reacts with ammonia water in the carbonization tower under the catalysis of sulfuric acid to prepare ammonium formate;
step 3, carrying out dimerization and dehydrogenation reactions on the ammonium formate generated in the step 2 to obtain ammonium oxalate monohydrate, and dehydrating the ammonium oxalate monohydrate to obtain anhydrous ammonium oxalate;
and 4, dehydrating the anhydrous ammonium oxalate obtained in the step 3 to obtain oxamide.
The invention is also characterized in that:
in the step 1, the removed carbon dioxide reacts with ammonia water to prepare ammonium bicarbonate.
In the step 2, the pressure of a compressor is increased to 1.7-1.9 Mpa, and heat conducting oil is heated to 175-185 ℃, wherein the temperature of the middle upper part in the carbonization tower is 175-185 ℃, and the temperature of the bottom part is 65-95 ℃; the concentration of the ammonia water is 25-50%, and the molar ratio of the ammonia water to the sulfuric acid is 1.5-2.5: 1.
In step 3, the temperature for dehydrating the ammonium monohydrochloride is 95 ℃.
In the step 4, the temperature for dehydrating the anhydrous ammonium oxalate is 180-200 ℃.
The compressor adopts a red flag board compressor or a 6L2K compressor.
The invention has the beneficial effects that: the invention relates to a method for producing oxamide by utilizing a synthetic ammonia-ammonium bicarbonate coproduction process, which utilizes a synthetic ammonia-ammonium bicarbonate joint production process to desulfurize semi-water gas, compress, remove carbon dioxide, recompress and remove carbon monoxide, utilizes the reaction of the carbon monoxide and ammonia water under the catalysis of sulfuric acid to generate ammonium formate, and then generates anhydrous ammonium oxalate through dimerization, dehydrogenation and dehydration, and the anhydrous ammonium oxalate is dehydrated to obtain the oxamide.
Drawings
FIG. 1 is a process flow diagram of the process of removing carbon monoxide and generating oxamide in an oxamide workshop for producing oxamide by using the ammonia synthesis-ammonium bicarbonate coproduction process.
In the figure, 1, a main carbonization tower, 2, a secondary carbonization tower, 3, a fixed secondary tower, 4, a cooling tower, 5, a recovery cleaning tower, 6, a circulating pump, 7, a concentrated ammonia pump, 8, a clean water pump, 9, a thickener, 10, a centrifuge, 11, a mother liquor barrel, 12, an ammonia suction pump, 13, a dilute ammonia water storage tank, 14, a high-level ammonia suction device, 15, a cooling discharge pipe, 16, a concentrated ammonia water storage tank, 17, an acid adding tank, 18, an acid liquid pump and 19, a sulfuric acid liquid tank are arranged in sequence.
Detailed Description
The invention is described in detail below with reference to the drawings and the detailed description.
The invention discloses a method for producing oxamide by utilizing a process of ammonia synthesis and ammonium bicarbonate coproduction, which is specifically implemented according to the following steps as shown in figure 1:
step 1, utilizing a process of ammonia synthesis and ammonium bicarbonate coproduction to produce the semi-hydrated coal produced in a gas making workshopQi (H)236-37，CO32-35，N221-22，CO26-9) feeding the semi-water gas into a gas holder, pumping the semi-water gas in the gas holder by using a Roots blower, desulfurizing the semi-water gas, feeding the semi-water gas into a first section and a second section of a compressor, compressing the semi-water gas to 0.7Mpa, cooling the semi-water gas to room temperature, canceling a conversion section, and directly feeding the semi-water gas into a carbonization workshop to remove carbon dioxide to obtain a feed gas; reacting the removed carbon dioxide with ammonia water to prepare ammonium bicarbonate;
Step 2, three-section pressure of the raw material gas obtained in the step 1 is increased to 1.7-1.9 Mpa through a compressor, the raw material gas with the increased pressure is heated to 175-185 ℃ by using heat conduction oil, and then the raw material gas enters a carbonization tower (a main tower 1 or a secondary tower 2) of an oxamide workshop, the temperature of the middle upper part in the carbonization tower (the main tower 1 or the secondary tower 2) is 175-185 ℃, the temperature of the bottom is 65-95 ℃, namely under the condition that carbon monoxide in the raw material gas does not run high, the reaction temperature of the middle upper part is controlled according to the lower limit temperature of 175 ℃, and the temperature of the bottom is controlled according to the lower limit temperature of 65 ℃; under the condition that carbon monoxide in raw material gas runs high, the reaction temperature of the middle upper part is controlled according to the upper limit temperature of 185 ℃, and the temperature of the bottom part is controlled according to the upper limit temperature of 95 ℃; reacting carbon monoxide in the raw material gas with ammonia water in a carbonization tower under the catalysis of sulfuric acid to prepare ammonium formate;
wherein the concentration of the ammonia water is 25-50%, and the molar ratio of the ammonia water to the sulfuric acid is 1.5-2.5: 1;
step 3, carrying out dimerization and dehydrogenation reactions on the ammonium formate generated in the step 2 to obtain ammonium monohydrochloride, and dehydrating the ammonium monohydrochloride at the temperature of 95 ℃ to obtain anhydrous ammonium oxalate;
2HCOONH4+H2O——→(COONH4)2·H2O+H2(dimeric dehydrogenation)
Step 4, dehydrating the anhydrous ammonium oxalate obtained in the step 3 at the temperature of between 180 and 200 ℃ to obtain oxamide;
The raw material gas from which carbon monoxide is removed in the step 2 is compressed to 12Mpa by four or five sections of a compressor according to the original ammonia synthesis process, toxic gases are removed by copper washing and copper acetate ammonia liquid, then the raw material gas is compressed to 32Mpa by six sections of the compressor, and hydrogen and nitrogen are synthesized into ammonia.
As shown in fig. 1, the preparation of ammonium sulfide water, the recovery of mother liquor, the recovery of ammonia in raw material gas and the like in an oxamide workshop can be set according to the process equipment for producing ammonium bicarbonate by using original synthetic ammonia, and the preparation process of the ammonium sulfide water is completed by a circulating pump 6, a concentrated ammonia pump 7, a clean water pump 8, a thickener 9, a centrifuge 10, a mother liquor barrel 11, an ammonia suction pump 12, a dilute ammonia water storage tank 13, a high-level ammonia suction device 14, a cooling calandria 15, a concentrated ammonia water storage tank 16, an acid adding tank 17, an acid liquid pump 18 and sulfuric acid liquid 19; mother liquor obtained by the thickener 9 and the centrifuge is recycled to the mother liquor barrel 11 of the absorption section for reuse, and sulfuric acid can be directly added into the acid adding tank 17 after being added.
In the present invention, CO and NH3·H2The absorption neutralization reaction of O is the key to the reaction in the production of oxamide, NH3·H2O is actually ammonia monohydrate, and is alkaline. The ammonia is dissolved in water to form mostly ammonia monohydrate, and NH is contained in the ammonia water4 +The component (b) is only 1% and hardly reacts with CO. So that the electrolyte sulfuric acid must be added as a catalyst to convert the ammonia water into NH 4+And OH-The bond capable of breaking with CO undergoes a nucleophilic addition reaction with carbonyl, recombining to ammonium formate.
Since the reaction of carbon monoxide with ammonium hydroxide requires the breaking of the CO molecular bond to form a carbonyl group, which is then reacted with NH4 +And OH-The nucleophilic addition reaction of carbonyl is carried out, and ammonium formate is recombined, which belongs to endothermic reaction and needs certain pressure. Therefore, the pressure of the feed gas at the three-stage outlet of the compressor is required to meet 1.7-1.9 Mpa, and the temperature is also required to reach 175-18 DEG CThe reaction temperature is 5 ℃, but the outlet temperature of the three sections of the compressor is only about 125 ℃, so the gas needs to be circularly heated by heat-conducting oil and an electric heater to ensure that the temperature reaches the reaction temperature of 175-185 ℃, the carbonization tower is different from a carbonization tower for absorbing carbon dioxide, needs to be cooled and heated or insulated, a copper pipe is adopted for circulating by a circulating pipe of the carbonization tower, and the heat-conducting oil is added into the copper pipe to provide heat. The temperature of each part of the carbonization tower was adjusted depending on the reaction. The temperature of the middle upper part of the carbonization tower can be controlled to be 175-185 ℃, the ammonium formate in the main reaction zone at the bottom of the carbonization tower is subjected to dimerization, dehydrogenation and dehydration, most of the ammonium formate forms an oxamide finished product, and the ammonium formate is taken out when waiting to be taken out, and the temperature is controlled to be 65-95 ℃. The temperature of each part of the carbonization tower can be controlled according to the lower limit under the condition that the index of the carbon monoxide in the raw material gas is not increased.
The compressor selects a machine type which is relatively close to the reaction pressure condition as the equipment of the invention, wherein the red flag plate compressor has a two-section outlet of 0.68Mpa and a three-section outlet of 1.86 Mpa; a 6L2K compressor, a second-stage outlet of 0.74Mpa, a third-stage outlet of 1.89Mpa or 1 gamma-266/320 compressor, and a second-stage outlet of 1.18Mpa, which directly enters an oxamide workshop to prepare the oxamide without three-stage compression (probably because of low pressure and slow reaction speed).
Example 1
The invention relates to a method for producing oxamide by utilizing a process of ammonia synthesis and ammonium bicarbonate coproduction, which is implemented according to the following steps:
step 1, utilizing a process of synthesizing ammonia and coproducing ammonium bicarbonate to produce semi-water gas (H) produced in a gas-making workshop236-37，CO32-35，N221-22，CO26-9) feeding the semi-water gas into a gas holder, pumping the semi-water gas in the gas holder by a Roots blower, desulfurizing the semi-water gas, feeding the semi-water gas into a first section and a second section of a compressor, compressing the semi-water gas to 0.7Mpa, cooling the semi-water gas to room temperature, removing a conversion section, and directly feeding the semi-water gas into a carbonization workshop to remove carbon dioxide to obtain a feed gas; reacting the removed carbon dioxide with ammonia water to prepare ammonium bicarbonate;
step 2, raising the pressure of the raw material gas obtained in the step 1 to 1.8Mpa through a compressor by three sections, heating the raw material gas with the raised pressure to 180 ℃ by using heat conduction oil, then feeding the raw material gas into a carbonization tower of an oxamide workshop, wherein the temperature of the middle upper part in the carbonization tower is 180 ℃, the temperature of the bottom is 80 ℃, and carbon monoxide in the raw material gas reacts with ammonia water in the carbonization tower under the catalysis of sulfuric acid to prepare ammonium formate;
Wherein the concentration of the ammonia water is 40%, and the molar ratio of the ammonia water to the sulfuric acid is 2: 1;
step 3, carrying out dimerization and dehydrogenation reactions on the ammonium formate generated in the step 2 to obtain ammonium monohydrochloride, and dehydrating the ammonium monohydrochloride at the temperature of 95 ℃ to obtain anhydrous ammonium oxalate;
2HCOONH4+H2O——→(COONH4)2·H2O+H2(dimeric dehydrogenation)
Step 4, dehydrating the anhydrous ammonium oxalate obtained in the step 3 at the temperature of 190 ℃ to obtain oxamide;
example 2
The invention relates to a method for producing oxamide by utilizing a process of ammonia synthesis and ammonium bicarbonate coproduction, which is implemented according to the following steps:
step 1, utilizing a process of synthesizing ammonia and coproducing ammonium bicarbonate to produce semi-water gas (H) produced in a gas-making workshop236-37，CO32-35，N221-22，CO26-9) feeding the semi-water gas into a gas holder, pumping the semi-water gas in the gas holder by a Roots blower, desulfurizing the semi-water gas, feeding the semi-water gas into a first section and a second section of a compressor, compressing the semi-water gas to 0.7Mpa, cooling the semi-water gas to room temperature, and feeding the semi-water gas into a carbonization workshop to remove carbon dioxide to obtain feed gas; reacting the removed carbon dioxide with ammonia water to prepare ammonium bicarbonate;
step 2, three-section pressure of the raw material gas obtained in the step 1 is increased to 1.7Mpa through a compressor, the raw material gas with the increased pressure is heated to 185 ℃ through heat conduction oil, and then the raw material gas enters a carbonization tower of an oxamide workshop, wherein the temperature of the middle upper part in the carbonization tower is 185 ℃, the temperature of the bottom part is 95 ℃, and under the condition that carbon monoxide in the raw material gas runs high, the reaction temperature of the middle upper part is controlled according to the lower limit temperature of 185 ℃, and the temperature of the bottom part is controlled according to the lower limit temperature of 95 ℃; reacting carbon monoxide in the raw material gas with ammonia water in a carbonization tower under the catalysis of sulfuric acid to prepare ammonium formate;
Wherein the concentration of the ammonia water is 50%, and the molar ratio of the ammonia water to the sulfuric acid is 1.5: 1;
step 3, carrying out dimerization and dehydrogenation reactions on the ammonium formate generated in the step 2 to obtain ammonium monohydrochloride, and dehydrating the ammonium monohydrochloride at the temperature of 95 ℃ to obtain anhydrous ammonium oxalate;
2HCOONH4+H2O——→(COONH4)2·H2O+H2(dimeric dehydrogenation)
Step 4, dehydrating the anhydrous ammonium oxalate obtained in the step 3 at the temperature of 180 ℃ to obtain oxamide;
example 3
The invention relates to a method for producing oxamide by utilizing a process of ammonia synthesis and ammonium bicarbonate coproduction, which is implemented according to the following steps:
step 1, utilizing a process of synthesizing ammonia and coproducing ammonium bicarbonate to produce semi-water gas (H) produced in a gas-making workshop236-37，CO32-35，N221-22，CO26-9) feeding the semi-water gas into a gas holder, pumping the semi-water gas in the gas holder by a Roots blower, desulfurizing the semi-water gas, feeding the semi-water gas into a first section and a second section of a compressor, compressing the semi-water gas to 0.7Mpa, cooling the semi-water gas to room temperature, and feeding the semi-water gas into a carbonization workshop to remove carbon dioxide to obtain feed gas; reacting the removed carbon dioxide with ammonia water to prepare ammonium bicarbonate;
step 2, three-section pressure lifting is carried out on the raw material gas obtained in the step 1 to 1.9Mpa through a compressor, heat conducting oil is used for heating the raw material gas with the pressure lifted to 175 ℃, and the raw material gas enters a carbonization tower of an oxamide workshop, wherein the temperature of the middle upper part in the carbonization tower is 175 ℃, and the temperature of the bottom part is 65 ℃, namely under the condition that carbon monoxide in the raw material gas does not run high, the reaction temperature of the middle upper part is controlled according to the lower limit temperature of 175 ℃, and the temperature of the bottom part is controlled according to the lower limit temperature of 65 ℃; reacting carbon monoxide in the raw material gas with ammonia water in a carbonization tower (a main carbonization tower 1 or a subsidiary carbonization tower 2) under the catalysis of sulfuric acid to prepare ammonium formate;
Wherein the concentration of the ammonia water is 25 percent, and the molar ratio of the ammonia water to the sulfuric acid is 2.5: 1;
step 3, carrying out dimerization and dehydrogenation reactions on the ammonium formate generated in the step 2 to obtain ammonium monohydrochloride, and dehydrating the ammonium monohydrochloride at the temperature of 95 ℃ to obtain anhydrous ammonium oxalate;
2HCOONH4+H2O——→(COONH4)2·H2O+H2(dimeric dehydrogenation)
Step 4, dehydrating the anhydrous ammonium oxalate obtained in the step 3 at the temperature of 200 ℃ to obtain oxamide;
example 4
The invention relates to a method for producing oxamide by utilizing a process of ammonia synthesis and ammonium bicarbonate coproduction, which is implemented according to the following steps:
step 1, utilizing a process of synthesizing ammonia and coproducing ammonium bicarbonate to produce semi-water gas (H) produced in a gas-making workshop236-37，CO32-35，N221-22，CO26-9) feeding the semi-water gas into a gas holder, pumping the semi-water gas in the gas holder by a Roots blower, desulfurizing the semi-water gas, feeding the semi-water gas into a first section and a second section of a compressor, compressing the semi-water gas to 0.7Mpa, cooling the semi-water gas to room temperature, and feeding the semi-water gas into a carbonization workshop to remove carbon dioxide to obtain feed gas; reacting the removed carbon dioxide with ammonia water to prepare ammonium bicarbonate;
step 2, the pressure of the raw material gas obtained in the step 1 is increased to 1.85Mpa through a compressor in three sections, the raw material gas with the increased pressure is heated to 180 ℃ by using heat conduction oil and then enters a carbonization tower of an oxamide workshop, the temperature of the middle upper part in the carbonization tower is 180 ℃, the temperature of the bottom is 90 ℃, and carbon monoxide in the raw material gas reacts with ammonia water in the carbonization tower under the catalysis of sulfuric acid to prepare ammonium formate;
Wherein the concentration of the ammonia water is 45 percent, and the molar ratio of the ammonia water to the sulfuric acid is 2.3: 1;
step 3, carrying out dimerization and dehydrogenation reactions on the ammonium formate generated in the step 2 to obtain ammonium monohydrochloride, and dehydrating the ammonium monohydrochloride at the temperature of 95 ℃ to obtain anhydrous ammonium oxalate;
2HCOONH4+H2O——→(COONH4)2·H2O+H2(dimeric dehydrogenation)
Step 4, dehydrating the anhydrous ammonium oxalate obtained in the step 3 at the temperature of 195 ℃ to obtain oxamide;
example 5
The invention relates to a method for producing oxamide by utilizing a process of ammonia synthesis and ammonium bicarbonate coproduction, which is implemented according to the following steps:
step 1, utilizing a process of synthesizing ammonia and coproducing ammonium bicarbonate to produce semi-water gas (H) produced in a gas-making workshop236-37，CO32-35，N221-22，CO26-9) feeding the semi-water gas into a gas holder, pumping the semi-water gas in the gas holder by a Roots blower, desulfurizing the semi-water gas, feeding the semi-water gas into a first section and a second section of a compressor, compressing the semi-water gas to 0.7Mpa, cooling the semi-water gas to room temperature, removing a conversion section, and directly feeding the semi-water gas into a carbonization workshop to remove carbon dioxide to obtain a feed gas; reacting the removed carbon dioxide with ammonia water to prepare ammonium bicarbonate;
step 2, raising the pressure of the raw material gas obtained in the step 1 to 1.75Mpa through a compressor in three sections, heating the raw material gas with the raised pressure to 182 ℃ by using heat conduction oil, then entering a carbonization tower of an oxamide workshop, wherein the temperature of the middle upper part in the carbonization tower is 182 ℃, the temperature of the bottom part in the carbonization tower is 70 ℃, and reacting carbon monoxide in the raw material gas with ammonia water in the carbonization tower under the catalysis of sulfuric acid to prepare ammonium formate;
Wherein the concentration of the ammonia water is 30 percent, and the molar ratio of the ammonia water to the sulfuric acid is 1.7: 1;
step 3, carrying out dimerization and dehydrogenation reactions on the ammonium formate generated in the step 2 to obtain ammonium monohydrochloride, and dehydrating the ammonium monohydrochloride at the temperature of 95 ℃ to obtain anhydrous ammonium oxalate;
2HCOONH4+H2O——→(COONH4)2·H2O+H2(dimeric dehydrogenation)
Step 4, dehydrating the anhydrous ammonium oxalate obtained in the step 3 at the temperature of 185 ℃ to obtain oxamide;
the invention relates to a method for producing oxamide by utilizing a process of synthesizing ammonia and coproducing ammonium bicarbonate, which is characterized in that a combined production process of synthesizing ammonia and ammonium bicarbonate is utilized, sodium formate is prepared by referring to a traditional process of preparing formic acid by absorbing and neutralizing carbon monoxide and caustic soda, then ammonium oxalate is prepared by referring to a process of preparing oxalic acid by a sodium formate method, oxalic acid and ammonia water react to prepare ammonium oxalate, and finally the ammonium oxalate is prepared into the oxamide by a pyrolysis method; namely, the semi-water gas is desulfurized, compressed, deprived of carbon dioxide, recompressed and deprived of carbon monoxide, the carbon monoxide reacts with ammonia water under the catalysis of sulfuric acid to generate ammonium formate, then the ammonium oxalate is dehydrated through dimerization, dehydrogenation and dehydration to generate anhydrous ammonium oxalate, and the anhydrous ammonium oxalate is dehydrated to obtain the oxamide, the method for producing the oxamide fully utilizes the mature and unique synthetic ammonia-ammonium bicarbonate combined production process in China, the carbon monoxide reacts with the ammonia water to prepare the oxamide which is used as another decarburization technology for synthesizing ammonia, the process transformation technology is simple, the manufacturing operation of the oxamide is easy to grasp, the production cost of the oxamide can be reduced to about 1000 yuan/ton, the production and the popularization of the environment-friendly fertilizer are greatly facilitated, the deprived carbon dioxide in the preparation process can react with the ammonia water to generate ammonium bicarbonate, the feed gas deprived of the carbon monoxide is processed according to the original synthetic ammonia, the ammonia is synthesized from the hydrogen and the nitrogen, so that the waste gas can be effectively treated, and no pollution is caused.
Claims (6)
1. A method for producing oxamide by utilizing a process of ammonia synthesis and ammonium bicarbonate coproduction is characterized by comprising the following steps:
step 1, feeding semi-water gas produced in a gas making workshop into a gas holder by utilizing a synthetic ammonia-ammonium bicarbonate coproduction process, pumping the semi-water gas in the gas holder by using a Roots blower, desulfurizing the semi-water gas, then feeding the semi-water gas into a first section and a second section of a compressor to be compressed to 0.7Mpa, cooling the semi-water gas to room temperature, canceling a conversion section, and directly feeding the semi-water gas into a carbonization workshop to remove carbon dioxide to obtain feed gas;
step 2, the pressure of the raw material gas obtained in the step 1 is increased through a compressor in three sections, the raw material gas with the increased pressure is heated by using heat conduction oil and then enters a carbonization tower of an oxamide workshop, and carbon monoxide in the raw material gas reacts with ammonia water in the carbonization tower under the catalysis of sulfuric acid to prepare ammonium formate;
step 3, carrying out dimerization and dehydrogenation reactions on the ammonium formate generated in the step 2 to obtain ammonium oxalate monohydrate, and dehydrating the ammonium oxalate monohydrate to obtain anhydrous ammonium oxalate;
and 4, dehydrating the anhydrous ammonium oxalate obtained in the step 3 to obtain oxamide.
2. The method for producing oxamide by using the synthetic ammonia-ammonium bicarbonate coproduction process according to claim 1, wherein the carbon dioxide removed in the step 1 is reacted with ammonia water to produce ammonium bicarbonate.
3. The method for producing oxamide by using a synthetic ammonia-co-production ammonium bicarbonate process according to claim 1, wherein in the step 2, the pressure of a compressor is increased to 1.7-1.9 Mpa, and heat conducting oil is heated to 175-185 ℃, wherein the temperature of the middle upper part in the carbonization tower is 175-185 ℃, and the temperature of the bottom part is 65-95 ℃; the concentration of the ammonia water is 25-50%, and the molar ratio of the ammonia water to the sulfuric acid is 1.5-2.5: 1.
4. The method for producing oxamide by the synthetic ammonia-ammonium bicarbonate coproduction process according to claim 1, wherein the temperature for dehydrating the ammonium monohydrochloride in the step 3 is 95 ℃.
5. The method for producing oxamide by using the synthetic ammonia-ammonium bicarbonate coproduction process according to claim 1, wherein the temperature for dehydrating the anhydrous ammonium oxalate in the step 4 is 180-200 ℃.
6. The method for producing oxamide by the ammonia synthesis-ammonium bicarbonate coproduction process according to claim 1, wherein the compressor is a red flag brand compressor or a 6L2K compressor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910610178.0A CN110272352B (en) | 2019-07-08 | 2019-07-08 | Method for producing oxamide by utilizing ammonia synthesis-ammonium bicarbonate coproduction process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910610178.0A CN110272352B (en) | 2019-07-08 | 2019-07-08 | Method for producing oxamide by utilizing ammonia synthesis-ammonium bicarbonate coproduction process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110272352A CN110272352A (en) | 2019-09-24 |
| CN110272352B true CN110272352B (en) | 2022-05-03 |
Family
ID=67962908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910610178.0A Active CN110272352B (en) | 2019-07-08 | 2019-07-08 | Method for producing oxamide by utilizing ammonia synthesis-ammonium bicarbonate coproduction process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110272352B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4379939A (en) * | 1980-04-04 | 1983-04-12 | Tennessee Valley Authority | Preparation of nitrogen fertilizers from oxalate esters prepared by the oxidative carbonylation of alcohols over noble metal catalysts utilizing regenerable 2,5-cyclohexadiene-1,4-dione oxidants |
| CN102267921A (en) * | 2011-05-26 | 2011-12-07 | 陈贻盾 | Continuous processing technology for synthesis of oxamide |
| CN104610087A (en) * | 2014-11-28 | 2015-05-13 | 西南化工研究设计院有限公司 | Device and method for purifying yellow phosphorus tail gas and continuously synthesizing oxamide |
| WO2018234999A1 (en) * | 2017-06-21 | 2018-12-27 | Sabic Global Technologies B.V. | Cesium oxalate production from cesium carbonate |
| CN110041218A (en) * | 2018-01-15 | 2019-07-23 | 中国科学院兰州化学物理研究所苏州研究院 | A kind of preparation method of oxamides |
-
2019
- 2019-07-08 CN CN201910610178.0A patent/CN110272352B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4379939A (en) * | 1980-04-04 | 1983-04-12 | Tennessee Valley Authority | Preparation of nitrogen fertilizers from oxalate esters prepared by the oxidative carbonylation of alcohols over noble metal catalysts utilizing regenerable 2,5-cyclohexadiene-1,4-dione oxidants |
| CN102267921A (en) * | 2011-05-26 | 2011-12-07 | 陈贻盾 | Continuous processing technology for synthesis of oxamide |
| CN104610087A (en) * | 2014-11-28 | 2015-05-13 | 西南化工研究设计院有限公司 | Device and method for purifying yellow phosphorus tail gas and continuously synthesizing oxamide |
| WO2018234999A1 (en) * | 2017-06-21 | 2018-12-27 | Sabic Global Technologies B.V. | Cesium oxalate production from cesium carbonate |
| CN110041218A (en) * | 2018-01-15 | 2019-07-23 | 中国科学院兰州化学物理研究所苏州研究院 | A kind of preparation method of oxamides |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110272352A (en) | 2019-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102267921B (en) | A kind of synthesis oxamide continuous processing | |
| CN102585951B (en) | Process for co-production of liquefied synthesis gas, pure hydrogen and methanol from coke-oven gas | |
| CN114602406B (en) | Production device and production method of lithium hexafluorophosphate | |
| CN111153823B (en) | Method for preparing oxamide from dimethyl oxalate | |
| CN101492398B (en) | Urea production process of high-efficiency condensation, low-mounting height CO2 air stripping method and high-voltage lamp type full condensation reactor | |
| CN108383097B (en) | A method of utilizing extraction Wet-process Phosphoric Acid Production water solubility ammonium polyphosphate | |
| CN110272352B (en) | Method for producing oxamide by utilizing ammonia synthesis-ammonium bicarbonate coproduction process | |
| CN104610087B (en) | Device and method for purifying yellow phosphorus tail gas and continuously synthesizing oxamide | |
| CN100337994C (en) | Method for preparing composite fertilizer of potassium sulfate and ammonium | |
| CN103950952A (en) | Preparation method of high-purity deuterated ammonia | |
| CN103601630A (en) | Method utilizing calcium carbide slag and carbon monoxide to synthesize calcium formate | |
| CN108910914A (en) | One kind efficiently synthesizing ammonia production technology | |
| CN113582869B (en) | Process method for producing oxamide and methyl carbamate in series | |
| CN111995592B (en) | Method and device for co-production of urea and melamine | |
| CN215924409U (en) | Device for preparing biomass activated carbon and co-producing biomass synthesis gas through physical and chemical coupling activation | |
| CN213865389U (en) | System for utilize cement kiln tail waste gas and ardealite preparation ammonium sulfate | |
| CN110304638B (en) | Method for preparing cyanamide by using urea | |
| CN204981691U (en) | System for two segmentation carbide stove fine coal system ethylene | |
| CN1872842B (en) | Associated melamine from carbon ammonium through technique of two-step method under normal pressure | |
| CN103539689B (en) | Preparation method of formamide | |
| CN108707064B (en) | Production method for co-producing dimethyl ether by using blast furnace gas | |
| CN220472265U (en) | Potassium sulfate reaction furnace with preheating function | |
| CN103130247A (en) | Process for producing ammonium sulfate and hydrogen chloride by employing ammonium chloride and sulfuric acid | |
| CN202390347U (en) | Recycling system for methanol system separation water | |
| CN103664571A (en) | Method for synthesizing calcium formate by using industrial emission carbon monoxide exhaust gas through batch reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220330 Address after: 710075 Room 101, No. 23, Tuanjie South Road, high tech Zone, Xi'an, Shaanxi Province Applicant after: Shaanxi Tongze Human Settlement Engineering Technology Co.,Ltd. Address before: 710075 No. 1188, Eurasian Avenue, Chanba District, Xi'an City, Shaanxi Province Applicant before: Xi'an Tongze Xinsilk Road Agriculture Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |