CN110272352A - A method of oxamides is produced using synthesis ammonia-co-producing ammonium bicarbonate technique - Google Patents
A method of oxamides is produced using synthesis ammonia-co-producing ammonium bicarbonate technique Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/26—Carbonates or bicarbonates of ammonium
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- 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
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C51/41—Preparation of salts of carboxylic acids
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Abstract
Synthesis ammonia-co-producing ammonium bicarbonate technique production oxamides method is utilized the invention discloses a kind of, it follows the steps below to implement: step 1, utilize synthesis ammonia-co-producing ammonium bicarbonate technique, semiwater gas is sent into gas holder, semiwater gas in gas holder is extracted with Roots blower again and is compressed to 0.7Mpa into one section of compressor, two sections after desulfurization, after being cooled to room temperature, cancels conversion section, direct carbon dioxide removal, obtains unstripped gas；Step 2, unstripped gas is passed through into three sections of adherence pressures of compressor, then is heated unstripped gas with conduction oil, entered back into the carbonators of oxamides workshop, ammonium formate is made in the ammonium hydroxide in carbon monoxide and carbonators in unstripped gas under the catalysis of sulfuric acid；Step 3, ammonium formate is obtained into a water ammonium oxalate through double focusing, dehydrogenation, a water ammonium oxalate obtains anhydrous oxalic acid ammonium through dehydration；Step 4, oxamides is obtained after the dehydration of anhydrous oxalic acid ammonium.The oxamides of the method for the present invention production is at low cost, and production process is pollution-free, easy to operate.
Description
Technical field
The invention belongs to oxamides production method technical fields, and in particular to a kind of to utilize synthesis ammonia-co-producing ammonium bicarbonate
The method of technique production oxamides.
Background technique
Oxamides also known as oxamide, oxalamide.Molecular formula: (CONH2)2, nitrogenous 31.81%, white crystal, slightly soluble
It is almost insoluble in cold water in hot water and ethyl alcohol, 0.6 gram of solubility when 0.04 gram of solubility, 100 DEG C at 7 DEG C, 419 DEG C of fusing point,
Specific gravity 1.667, does not absorb water, nontoxic, can store in indefinite duration.
Agricultural practice proves that oxamides is a kind of excellent slow nitrogen fertilizer application, in numerous slowly/controlled releasing fertilizers, oxamides
((CONH2)2) have than broader development and application prospect, it is able to satisfy crop entire breeding time to the needs of nitrogen, reduces
Loss caused by the leaching loss of nitrogen, volatilization and denitrification improves chemical fertilizer utilization ratio, reduces fertilizer application frequency, saves manpower
And the time；The carbon of oxamides and ammonium hydrogen carbonate, nitrogen are capable of providing than and give plant suitable carbon-nitrogen ratio, meet crop simultaneously
Carbon-based nutritional need safeguards the ecological balance of soil, it is as good slow release fertilizer in application value agriculturally in Japan
It is confirmed already Deng area.It is just carried out early in the seventies Japanese agriculture technical research institute with the oxamides of hydrogen cyanide synthesis
Rice and wheat fertilizer test, to harvest yield, the stem number of crop, the spike number variation of crop and number of productive tiller percentage and harvest
The nitrogen content etc. of object has done comprehensive measurement and comparison result, has made the evaluation of certainty to the advantages of oxamides nitrogenous fertilizer.West Germany is conspicuous
Xi Site (Hoechst) company is also tested in the same time, it was demonstrated that oxamides can stablize offer in crop entire growth period
Suitable for the nutrient that crop needs, it is a kind of excellent Slowly release nitrogen fertilizer certainly, and chemical fertilizer utilization ratio is higher, therefore is expected to be likely to become
Substitute the best product of urea.
The preparation process of current existing oxamides mainly has following three kinds:
(1) with hydrogen cyanide (HCN) for raw material preparation method, HCN first generates cyanogen ((CN) :) through oxidation, then oxalyl is made through hydrolyzing
Amine.The method can be divided into Degussa method, phase modulus method, Asahi Chemical Industry's method and Hoechat method, in four kinds of methods, difference be oxidant,
Catalyst and technique are different, but are all with hydrogen cyanide (HCN) for raw material, and cost is too high.According to research reports, if with propylene
By-product in nitrile production is raw material, which economically may be possible, but not yet industrializes so far.And the method is the disadvantage is that hydrogen
Cyanic acid toxicity is big, at high cost, there are no industrialization report；
(2) pyrolysismethod uses ammonium oxalate or oxalic acid urea pyrolysis, can also obtain some oxamides, but the method is at high cost, does not have
With practical value, correlative study is less.
(3) oxalate diester ammonolysis process, the method are that Oxidation of Carbon Monoxide is coupled synthesis of oxalic acid diester, and oxalate diester is normal
Acted under normal pressure and temperature with ammonia and generate oxamides, conversion ratio up to 98% or more, the oxamides of generation through centrifugal dehydration, washing, do
After dry finished product oxamides, purity up to the pure standard of chemistry, yield up to 97% or more, such method carbon monoxide, ammonia and
Oxygen can synthesize oxamides, this froms the perspective of from raw material, and tool has an enormous advantage.In this two-step reaction, it is important to first step oxalic acid
The synthesis of diester, though external existing oxamides is used as the report of slow release fertilizer research, and it is raw because oxamides low cost can not be solved
The large-scale commercial applications supply problem of critical materials dimethyl oxalate needed for producing, there is not yet oxamides large-scale industrial production
Report.
Three of the above technique all leads to not realize industrialization large-scale production because cost is too high, therefore, developmental research grass
The production of amide low cost will be a big contribution of China's agricultural production, rapid development, the protection agriculture to China's industrial or agricultural is promoted
Industry ecological environment benefit is of great significance.
Summary of the invention
Synthesis ammonia-co-producing ammonium bicarbonate technique production oxamides method, solution are utilized the object of the present invention is to provide a kind of
The problem of existing oxamides high production cost of having determined.
The technical scheme adopted by the invention is that a kind of utilize synthesis ammonia-co-producing ammonium bicarbonate technique production oxamides
Method is specifically implemented according to the following steps:
Step 1, using synthesis ammonia-co-producing ammonium bicarbonate technique, the semiwater gas of gas making workshop production is sent into gas holder, then
Semiwater gas in gas holder is extracted with Roots blower and is compressed to 0.7Mpa into one section of compressor, two sections after desulfurization, is cooled to
After room temperature, cancel conversion section, is directly entered carbonization workshop carbon dioxide removal to get unstripped gas is arrived；
Step 2, unstripped gas step 1 obtained is by three sections of adherence pressures of compressor, using conduction oil by adherence pressure
Unstripped gas afterwards is heated, and is entered back into the carbonators of oxamides workshop, the ammonia in carbon monoxide and carbonators in unstripped gas
Water reacts under the catalysis of sulfuric acid, and ammonium formate is made；
Step 3, ammonium formate step 2 generated obtains a water ammonium oxalate, water ammonium oxalate warp through double focusing, dehydrogenation reaction
Dehydration obtains anhydrous oxalic acid ammonium；
Step 4, oxamides is obtained after step 3 obtains the dehydration of anhydrous oxalic acid ammonium.
The features of the present invention also characterized in that:
In step 1, the carbon dioxide of removing is reacted with ammonia water, and ammonium hydrogen carbonate is made.
In step 2, compressor adherence pressure to 1.7~1.9Mpa, heat-conducting oil heating is to 175 DEG C~185 DEG C, wherein carbon
Changing middle and upper part temperature in tower is 175 DEG C~185 DEG C, and bottom temp is 65 DEG C~95 DEG C；The concentration of ammonium hydroxide is 25~50%, ammonium hydroxide
Molar ratio with sulfuric acid is 1.5~2.5:1.
In step 3, the temperature of water ammonium oxalate dehydration is 95 DEG C.
In step 4, the temperature of anhydrous oxalic acid ammonium dehydration is 180 DEG C~200 DEG C.
Compressor uses red flag board compressor or 6L2K compressor.
The beneficial effects of the present invention are: the present invention is a kind of to utilize synthesis ammonia-co-producing ammonium bicarbonate technique production oxamides
Method, using synthesis ammonia-ammonium bicarbonate combined producing process, by semiwater gas desulphurizing, compression, carbon dioxide removal, recompression, removing
Carbon monoxide is reacted under sulfuric acid catalysis with ammonium hydroxide using carbon monoxide and generates ammonium formate, then is generated through double focusing, dehydrogenation, dehydration
Anhydrous oxalic acid ammonium obtains oxamides after the dehydration of anhydrous oxalic acid ammonium, cost is relatively low for the oxamides of the method for the present invention preparation, process letter
It is single, and the carbon dioxide of the removing in preparation process can react with ammonia water generation ammonium hydrogen carbonate, the unstripped gas of removal of carbon monoxide
According to former ammonia synthesis process, hydrogen and nitrogen are synthesized into ammonia, waste gases can be effectively treated, turn waste into wealth.
Detailed description of the invention
Fig. 1 is that the present invention is a kind of to be removed using synthesis ammonia-co-producing ammonium bicarbonate technique production oxamides oxamides workshop
Carbon monoxide simultaneously generates oxamides process flow chart.
In figure, 1. Main carbonization towers, 2. pairs of carbonators, 3. fixed pairs of towers, 4. cooling towers, 5. recovery and rinsing towers, 6. circulating pumps,
7. dense ammonia pump, 8. fresh water pumps, 9. thickeners, 10. centrifuges, 11. mother vats, 12. inhale ammonia pump, and 13. weak aqua ammonia storage tanks, 14. is high
Position ammonia absorber, 15. cooling coils, 16. concentrated ammonia liquor storage tanks, 17. acid adding slots, 18. acid pumps, 19. sulfuric acid liquid baths.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
The present invention is a kind of using synthesis ammonia-co-producing ammonium bicarbonate technique production oxamides method, as shown in Figure 1, specifically
It follows the steps below to implement:
Step 1, using synthesis ammonia-co-producing ammonium bicarbonate technique, the semiwater gas (H that gas making workshop is produced236-37,
CO32-35, N221-22, CO2It 6-9) is sent into gas holder, then extracts semiwater gas in gas holder with Roots blower and enters pressure after desulfurization
One section of contracting machine, two sections be compressed to 0.7Mpa, after being cooled to room temperature, cancel conversion section, be directly entered carbonization workshop removing dioxy
Change carbon to get unstripped gas is arrived；The carbon dioxide of removing reacts with ammonia water, and ammonium hydrogen carbonate is made；
Step 2, for unstripped gas step 1 obtained by three sections of adherence pressures of compressor to 1.7~1.9Mpa, use is thermally conductive
Oil carries out the unstripped gas after adherence pressure to be heated to 175 DEG C~185 DEG C, and entering back into oxamides workshop carbonators, (king-tower 1 is paid
Tower 2) in, carbonators (king-tower 1 or paying tower 2) interior middle and upper part temperature is 175 DEG C~185 DEG C, and bottom temp is 65 DEG C~95 DEG C, i.e.,
In the case that carbon monoxide in unstripped gas does not run height, middle and upper part reaction temperature is controlled according to 175 DEG C of lower limit temperature, bottom temperature
Degree is controlled according to 65 DEG C of lower limit；In the case that carbon monoxide in unstripped gas runs height, middle and upper part reaction temperature is according to ceiling temperature
185 DEG C of controls, bottom temp are controlled according to 95 DEG C of the upper limit；The ammonium hydroxide in carbon monoxide and carbonators in unstripped gas is in sulfuric acid
The lower reaction of catalysis, is made ammonium formate；
Wherein, the concentration of ammonium hydroxide is 25~50%, and the molar ratio of ammonium hydroxide and sulfuric acid is 1.5~2.5:1；
Step 3, ammonium formate step 2 generated obtains a water ammonium oxalate, a water ammonium oxalate 95 through double focusing, dehydrogenation reaction
Anhydrous oxalic acid ammonium is obtained through dehydration at a temperature of DEG C；
2HCOONH4+H2O——→(COONH4)2·H2O+H2(double focusing dehydrogenation)
Step 4, it obtains obtaining oxamides after anhydrous oxalic acid ammonium is dehydrated at a temperature of 180 DEG C~200 DEG C through step 3；
Unstripped gas through step 2 removal of carbon monoxide is compressed according to former ammonia synthesis process through four sections or five sections of compressor
To 12Mpa, after copper is washed and removes toxic gas with cuprammonia, then compressor is gone to be compressed to 32Mpa, hydrogen and nitrogen through six sections
Gas synthesizes ammonia.
As shown in Figure 1, vulcanization ammonium hydroxide preparation, disposing mother liquor, the recycling of ammonia etc. in unstrpped gas in oxamides workshop
Be configured according to the process equipment of former Ammonia Production ammonium hydrogen carbonate, vulcanization ammonium hydroxide preparation flow through circulating pump 6, dense ammonia pump 7,
Fresh water pump 8, centrifuge 10, mother vat 11, inhales ammonia pump 12, weak aqua ammonia storage tank 13, high-order ammonia absorber 14, cooling coil at thickener 9
15, it is completed in concentrated ammonia liquor storage tank 16, acid adding slot 17, acid pump 18, sulfuric acid liquid 19；Thickener 9 and the isolated mother of centrifuge
Liquid is recovered in absorption section mother vat 11 and reuses, and addition sulfuric acid can be added directly into acid adding slot 17.
In the present invention, CO and NH3·H2The absorption neutralization reaction of O is reacted in oxamides production, NH3·H2O
Actually one hydration ammonia, belongs to alkalinity.Ammonia is dissolved in water and largely forms a hydration ammonia, has NH in ammonium hydroxide4 +Ingredient only account for
1%, it can hardly be reacted with CO.So electrolyte sulfuric acid must be added as catalysis, so that ammonium hydroxide is converted into NH4+And OH-, energy
The key of enough and CO fracture, carries out carbonyl nucleophilic addition, reconfigures as ammonium formate.
Since carbon monoxide needs CO molecular scission with reacting for ammonium hydroxide, formed carbonyl, then again with NH4 +With
OH-Carbonyl nucleophilic addition is carried out, is reconfigured as ammonium formate, belongs to the endothermic reaction, and need certain pressure.Institute
With the unstripped gas of three sections of compressor outlets, not only pressure needs to meet 1.7~1.9Mpa, and temperature should also reach 175 DEG C~185
DEG C reaction temperature, but three sections of outlet temperatures of compressor only have 125 DEG C or so, so the gas must use conduction oil, electric heating
Device carries out circulation temperature raising, its temperature is made to reach 175 DEG C~185 DEG C of reaction temperature, which is different from absorbing carbon dioxide
Carbonators, need to cool, but need temperature raising or heat preservation, the circulation pipe of the carbonators is recycled using copper pipe,
Conduction oil is added in copper pipe, to provide heat.The temperature at each position of carbonators is adjusted since reaction is different.Carbonization
The middle and upper part temperature of tower can control between 175 DEG C~185 DEG C, the bottom of tower, and the ammonium formate of main reaction region passes through double focusing, takes off
Hydrogen, dehydration largely form oxamides finished product, wait it is to be removed, as long as temperature control to 65 DEG C~95 DEG C.In unstripped gas
In the case that carbon monoxide index does not run height, the temperature at each position of carbonators can be controlled by lower limit.
Compressor selects the type of relatively reaction pressure condition as equipment of the invention, wherein the compression of red flag board
Machine, second stage exit 0.68Mpa, three sections of outlet 1.86Mpa；6L2K compressor, second stage exit 0.74Mpa, three sections of outlet 1.89Mpa
Or 1 Γ -266/320 compressor, second stage exit 1.18Mpa are directly entered oxamides workshop without three sections of compressions and prepare oxalyl
Amine (may be low due to pressure, reaction speed is slower).
Embodiment 1
The present invention is a kind of using synthesis ammonia-co-producing ammonium bicarbonate technique production oxamides method, specifically according to following step
It is rapid to implement:
Step 1, using synthesis ammonia-co-producing ammonium bicarbonate technique, the semiwater gas (H that gas making workshop is produced236-37,
CO32-35, N221-22, CO2It 6-9) is sent into gas holder, then extracts semiwater gas in gas holder with Roots blower and enters pressure after desulfurization
One section of contracting machine, two sections be compressed to 0.7Mpa, after being cooled to room temperature, cancel conversion section, be directly entered carbonization workshop removing dioxy
Change carbon to get unstripped gas is arrived；The carbon dioxide of removing reacts with ammonia water, and ammonium hydrogen carbonate is made；
Step 2, unstripped gas step 1 obtained, will using conduction oil by three sections of adherence pressures of compressor to 1.8Mpa
Unstripped gas after adherence pressure carries out being heated to 180 DEG C, enters back into the carbonators of oxamides workshop, middle and upper part temperature in carbonators
It is 180 DEG C, bottom temp is 80 DEG C, and the carbon monoxide in unstripped gas reacts under the catalysis of sulfuric acid with the ammonium hydroxide in carbonators,
Ammonium formate is made；
Wherein, the concentration of ammonium hydroxide is 40%, and the molar ratio of ammonium hydroxide and sulfuric acid is 2:1；
Step 3, ammonium formate step 2 generated obtains a water ammonium oxalate, a water ammonium oxalate 95 through double focusing, dehydrogenation reaction
Anhydrous oxalic acid ammonium is obtained through dehydration under at a temperature of DEG C；
2HCOONH4+H2O——→(COONH4)2·H2O+H2(double focusing dehydrogenation)
Step 4, it obtains obtaining oxamides after anhydrous oxalic acid ammonium is dehydrated at a temperature of 190 DEG C through step 3；
Embodiment 2
The present invention is a kind of using synthesis ammonia-co-producing ammonium bicarbonate technique production oxamides method, specifically according to following step
It is rapid to implement:
Step 1, using synthesis ammonia-co-producing ammonium bicarbonate technique, the semiwater gas (H that gas making workshop is produced236-37,
CO32-35, N221-22, CO2It 6-9) is sent into gas holder, then extracts semiwater gas in gas holder with Roots blower and enters pressure after desulfurization
One section of contracting machine, two sections be compressed to 0.7Mpa, after being cooled to room temperature, into carbonization workshop carbon dioxide removal to get arrive unstripped gas；
The carbon dioxide of removing reacts with ammonia water, and ammonium hydrogen carbonate is made；
Step 2, unstripped gas step 1 obtained, will using conduction oil by three sections of adherence pressures of compressor to 1.7Mpa
Unstripped gas after adherence pressure carries out being heated to 185 DEG C, enters back into the carbonators of oxamides workshop, middle and upper part temperature in carbonators
It is 185 DEG C, bottom temp is 95 DEG C, and in the case that the carbon monoxide in unstripped gas runs height, middle and upper part reaction temperature is according to lower limit
185 DEG C of temperature controls, bottom temp are controlled according to 95 DEG C of lower limit；The ammonium hydroxide in carbon monoxide and carbonators in unstripped gas is in sulphur
It is reacted under the catalysis of acid, ammonium formate is made；
Wherein, the concentration of ammonium hydroxide is 50%, and the molar ratio of ammonium hydroxide and sulfuric acid is 1.5:1；
Step 3, ammonium formate step 2 generated obtains a water ammonium oxalate, a water ammonium oxalate 95 through double focusing, dehydrogenation reaction
Anhydrous oxalic acid ammonium is obtained through dehydration under at a temperature of DEG C；
2HCOONH4+H2O——→(COONH4)2·H2O+H2(double focusing dehydrogenation)
Step 4, it obtains obtaining oxamides after anhydrous oxalic acid ammonium is dehydrated at a temperature of 180 DEG C through step 3；
Embodiment 3
The present invention is a kind of using synthesis ammonia-co-producing ammonium bicarbonate technique production oxamides method, specifically according to following step
It is rapid to implement:
Step 1, using synthesis ammonia-co-producing ammonium bicarbonate technique, the semiwater gas (H that gas making workshop is produced236-37,
CO32-35, N221-22, CO2It 6-9) is sent into gas holder, then extracts semiwater gas in gas holder with Roots blower and enters pressure after desulfurization
One section of contracting machine, two sections be compressed to 0.7Mpa, after being cooled to room temperature, into carbonization workshop carbon dioxide removal to get arrive unstripped gas；
The carbon dioxide of removing reacts with ammonia water, and ammonium hydrogen carbonate is made；
Step 2, unstripped gas step 1 obtained, will using conduction oil by three sections of adherence pressures of compressor to 1.9Mpa
Unstripped gas after adherence pressure carries out being heated to 175 DEG C DEG C, enters back into the carbonators of oxamides workshop, middle and upper part temperature in carbonators
Degree is 175 DEG C, and bottom temp is 65 DEG C, i.e., in the case that the carbon monoxide in unstripped gas does not run height, middle and upper part reaction temperature
It is controlled according to 175 DEG C of lower limit temperature, bottom temp is controlled according to 65 DEG C of lower limit；Carbon monoxide and carbonators in unstripped gas is (main
Carbonators 1 or pay carbonators 2) in ammonium hydroxide reacted under the catalysis of sulfuric acid, be made ammonium formate；
Wherein, the concentration of ammonium hydroxide is 25%, and the molar ratio of ammonium hydroxide and sulfuric acid is 2.5:1；
Step 3, ammonium formate step 2 generated obtains a water ammonium oxalate, a water ammonium oxalate 95 through double focusing, dehydrogenation reaction
Anhydrous oxalic acid ammonium is obtained through dehydration under at a temperature of DEG C；
2HCOONH4+H2O——→(COONH4)2·H2O+H2(double focusing dehydrogenation)
Step 4, it obtains obtaining oxamides after anhydrous oxalic acid ammonium is dehydrated at a temperature of 200 DEG C through step 3；
Embodiment 4
The present invention is a kind of using synthesis ammonia-co-producing ammonium bicarbonate technique production oxamides method, specifically according to following step
It is rapid to implement:
Step 1, using synthesis ammonia-co-producing ammonium bicarbonate technique, the semiwater gas (H that gas making workshop is produced236-37,
CO32-35, N221-22, CO2It 6-9) is sent into gas holder, then extracts semiwater gas in gas holder with Roots blower and enters pressure after desulfurization
One section of contracting machine, two sections be compressed to 0.7Mpa, after being cooled to room temperature, into carbonization workshop carbon dioxide removal to get arrive unstripped gas；
The carbon dioxide of removing reacts with ammonia water, and ammonium hydrogen carbonate is made；
Step 2, unstripped gas step 1 obtained, will using conduction oil by three sections of adherence pressures of compressor to 1.85Mpa
Unstripped gas after adherence pressure carries out being heated to 180 DEG C, enters back into the carbonators of oxamides workshop, middle and upper part temperature in carbonators
It is 180 DEG C, bottom temp is 90 DEG C, and the carbon monoxide in unstripped gas reacts under the catalysis of sulfuric acid with the ammonium hydroxide in carbonators,
Ammonium formate is made；
Wherein, the concentration of ammonium hydroxide is 45%, and the molar ratio of ammonium hydroxide and sulfuric acid is 2.3:1；
Step 3, ammonium formate step 2 generated obtains a water ammonium oxalate, a water ammonium oxalate 95 through double focusing, dehydrogenation reaction
Anhydrous oxalic acid ammonium is obtained through dehydration under at a temperature of DEG C；
2HCOONH4+H2O——→(COONH4)2·H2O+H2(double focusing dehydrogenation)
Step 4, it obtains obtaining oxamides after anhydrous oxalic acid ammonium is dehydrated at a temperature of 195 DEG C through step 3；
Embodiment 5
The present invention is a kind of using synthesis ammonia-co-producing ammonium bicarbonate technique production oxamides method, specifically according to following step
It is rapid to implement:
Step 1, using synthesis ammonia-co-producing ammonium bicarbonate technique, the semiwater gas (H that gas making workshop is produced236-37,
CO32-35, N221-22, CO2It 6-9) is sent into gas holder, then extracts semiwater gas in gas holder with Roots blower and enters pressure after desulfurization
One section of contracting machine, two sections be compressed to 0.7Mpa, after being cooled to room temperature, cancel conversion section, be directly entered carbonization workshop removing dioxy
Change carbon to get unstripped gas is arrived；The carbon dioxide of removing reacts with ammonia water, and ammonium hydrogen carbonate is made；
Step 2, unstripped gas step 1 obtained, will using conduction oil by three sections of adherence pressures of compressor to 1.75Mpa
Unstripped gas after adherence pressure carries out being heated to 182 DEG C, enters back into the carbonators of oxamides workshop, middle and upper part temperature in carbonators
It is 182 DEG C, bottom temp is 70 DEG C, and the carbon monoxide in unstripped gas reacts under the catalysis of sulfuric acid with the ammonium hydroxide in carbonators,
Ammonium formate is made；
Wherein, the concentration of ammonium hydroxide is 30%, and the molar ratio of ammonium hydroxide and sulfuric acid is 1.7:1；
Step 3, ammonium formate step 2 generated obtains a water ammonium oxalate, a water ammonium oxalate 95 through double focusing, dehydrogenation reaction
Anhydrous oxalic acid ammonium is obtained through dehydration under at a temperature of DEG C；
2HCOONH4+H2O——→(COONH4)2·H2O+H2(double focusing dehydrogenation)
Step 4, it obtains obtaining oxamides after anhydrous oxalic acid ammonium is dehydrated at a temperature of 185 DEG C through step 3；
The present invention is a kind of using synthesis ammonia-co-producing ammonium bicarbonate technique production oxamides method, utilizes synthesis ammonia-ammonium bicarbonate
Combined producing process absorbs the technique for neutralizing legal system formic acid referring to traditional carbon monoxide and caustic soda, sodium formate is made, then join
It according to sodium formate legal system oxalic acid technique, then is reacted with oxalic acid and ammonium hydroxide and ammonium oxalate is made, grass finally is made in ammonium oxalate pyrolysismethod
Amide；That is, semiwater gas desulphurizing, compression, carbon dioxide removal, recompression, removal of carbon monoxide are utilized carbon monoxide and ammonia
Water reacts under sulfuric acid catalysis generates ammonium formate, then generates anhydrous oxalic acid ammonium, the dehydration of anhydrous oxalic acid ammonium through double focusing, dehydrogenation, dehydration
After obtain oxamides, the method that the present invention produces oxamides is sufficiently used that China is mature, unique synthesis ammonia-bicarbonate
Ammonium combined producing process is reacted with carbon monoxide and ammonium hydroxide and oxamides is made, and as another decarburization technique of synthesis ammonia, technique changes
Make technically simple, oxamides manufacturing operation is easily mastered, and the production cost of oxamides can be down to 1000 yuan/ton or so, very
Be conducive to the production and popularization of this environment-friendly fertilizer, and the carbon dioxide of the removing in preparation process can react with ammonia water generation carbon
Hydrogen and nitrogen are synthesized ammonia according to former ammonia synthesis process, can be effectively treated by sour hydrogen ammonium, the unstripped gas of removal of carbon monoxide
Waste gases, it is pollution-free.
Claims (6)
1. a kind of utilize synthesis ammonia-co-producing ammonium bicarbonate technique production oxamides method, which is characterized in that specifically according to following
Step is implemented:
Step 1, using synthesis ammonia-co-producing ammonium bicarbonate technique, the semiwater gas of gas making workshop production is sent into gas holder, then use sieve
Thatch air blower extracts semiwater gas in gas holder and is compressed to 0.7Mpa into one section of compressor, two sections after desulfurization, is cooled to room temperature
Afterwards, cancel conversion section, be directly entered carbonization workshop carbon dioxide removal to get unstripped gas is arrived；
Step 2, unstripped gas step 1 obtained, will be after adherence pressure using conduction oil by three sections of adherence pressures of compressor
Unstripped gas is heated, and is entered back into the carbonators of oxamides workshop, and the ammonium hydroxide in carbon monoxide and carbonators in unstripped gas exists
It is reacted under the catalysis of sulfuric acid, ammonium formate is made；
Step 3, ammonium formate step 2 generated obtains a water ammonium oxalate, a water ammonium oxalate is through being dehydrated through double focusing, dehydrogenation reaction
Obtain anhydrous oxalic acid ammonium；
Step 4, oxamides is obtained after step 3 obtains the dehydration of anhydrous oxalic acid ammonium.
2. a kind of using synthesis ammonia-co-producing ammonium bicarbonate technique production oxamides method according to claim 1, feature exists
In in the step 1, the carbon dioxide of removing is reacted with ammonia water, and ammonium hydrogen carbonate is made.
3. a kind of using synthesis ammonia-co-producing ammonium bicarbonate technique production oxamides method according to claim 1, feature exists
In in the step 2, compressor adherence pressure to 1.7~1.9Mpa, heat-conducting oil heating is to 175 DEG C~185 DEG C, wherein carbonization
Middle and upper part temperature is 175 DEG C~185 DEG C in tower, and bottom temp is 65 DEG C~95 DEG C；The concentration of ammonium hydroxide be 25~50%, ammonium hydroxide with
The molar ratio of sulfuric acid is 1.5~2.5:1.
4. a kind of using synthesis ammonia-co-producing ammonium bicarbonate technique production oxamides method according to claim 1, feature exists
In in the step 3, the temperature of water ammonium oxalate dehydration is 95 DEG C.
5. a kind of using synthesis ammonia-co-producing ammonium bicarbonate technique production oxamides method according to claim 1, feature exists
In in the step 4, the temperature of anhydrous oxalic acid ammonium dehydration is 180 DEG C~200 DEG C.
6. a kind of using synthesis ammonia-co-producing ammonium bicarbonate technique production oxamides method according to claim 1, feature exists
In the compressor uses red flag board compressor or 6L2K compressor.
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| 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 |
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| 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 |
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