CN103086400B - Periodic off-gases is utilized to produce the environment-friendly clean process method of hydrocyanic acid derivant - Google Patents
Periodic off-gases is utilized to produce the environment-friendly clean process method of hydrocyanic acid derivant Download PDFInfo
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- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 title claims abstract description 244
- 239000007789 gas Substances 0.000 title claims abstract description 199
- 230000000737 periodic Effects 0.000 title claims abstract description 55
- 241001597008 Nomeidae Species 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000004140 cleaning Methods 0.000 title claims abstract description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 206
- 230000002194 synthesizing Effects 0.000 claims abstract description 152
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 113
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 111
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 110
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 103
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 47
- MNWBNISUBARLIT-UHFFFAOYSA-N Sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000007864 aqueous solution Substances 0.000 claims abstract description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 29
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 28
- LTYRAPJYLUPLCI-UHFFFAOYSA-N 2-hydroxyacetonitrile Chemical compound OCC#N LTYRAPJYLUPLCI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000010521 absorption reaction Methods 0.000 claims abstract description 26
- 238000004176 ammonification Methods 0.000 claims abstract description 21
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 238000004064 recycling Methods 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims description 28
- 150000002431 hydrogen Chemical class 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 9
- JMANVNJQNLATNU-UHFFFAOYSA-N Cyanogen Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract description 6
- JKNDTQVYGQBATP-UHFFFAOYSA-N argon;methane Chemical compound C.[Ar] JKNDTQVYGQBATP-UHFFFAOYSA-N 0.000 abstract description 3
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 abstract 2
- 238000011084 recovery Methods 0.000 description 23
- 239000000047 product Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 19
- LFVGISIMTYGQHF-UHFFFAOYSA-N Ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 15
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 15
- 239000012535 impurity Substances 0.000 description 15
- 235000019837 monoammonium phosphate Nutrition 0.000 description 15
- BFNBIHQBYMNNAN-UHFFFAOYSA-N Ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 12
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 12
- 235000011130 ammonium sulphate Nutrition 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 9
- 239000003345 natural gas Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- -1 synthesis ammonia Chemical compound 0.000 description 5
- XLJMAIOERFSOGZ-UHFFFAOYSA-N 420-05-3 Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- QVLTXCYWHPZMCA-UHFFFAOYSA-K phosphoric acid;phosphate Chemical compound OP(O)(O)=O.[O-]P([O-])([O-])=O QVLTXCYWHPZMCA-UHFFFAOYSA-K 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 241001076960 Argon Species 0.000 description 2
- 235000013876 argon Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005039 chemical industry Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001590 oxidative Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000003009 desulfurizing Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Abstract
What the present invention provided utilizes periodic off-gases to produce the environment-friendly clean process method of hydrocyanic acid derivant.It is characterized in that: the periodic off-gases containing methane is carried out isolated ammonia (or methanol), hydrogen, nitrogen, methane gas and tail gas by pressure-swing absorption apparatus and other separation equipment, ammonia (or methanol), hydrogen, nitrogen return synthesis ammonia (or synthesizing methanol) system and make full use of, methane gas is used for synthesizing hydrocyanic acid derivant, and tail gas is for the recycling of argon；Methane gas synthesis hydrocyanic acid is used for synthesizing various hydrocyanic acid derivant: methane gas is directly used in ammoxidation or ammonification dehydrogenation synthesis hydrocyanic acid synthesis gas, and synthesis gas and sodium hydrate aqueous solution absorb reaction and obtain Cyanogran. for synthesizing downstream hydrocyanic acid derivant, synthesis gas and formaldehyde and other organic aldehyde class synthesis of hydroxy acetonitrile and other hydrocyanic acid derivant for synthesizing downstream hydrocyanic acid derivant, synthesis gas water or other solvent absorption and resolving purification and obtain liquid hydrocyanic acid and for synthesizing downstream hydrocyanic acid derivant.
Description
Technical field
A kind of method relating to producing hydrocyanic acid derivant, refers to that the environmental protection utilizing periodic off-gases production hydrocyanic acid derivant is clear
Clean process, fully takes into account the periodic off-gases containing methane gas that the devices such as synthesis ammonia, synthesizing methanol and ammonia and methanol integrated production produce
Recovery and the feature of environmental protection of comprehensive cyclic utilization and production hydrocyanic acid derivant technical process, the environmental protection belonging to comprehensive utilization of resources is clear
Clean production method.
Background technology
Synthesis ammonia, synthesizing methanol and ammonia and methanol integrated production industry are well known industries, the group of synthetic ammonia installation periodic off-gases
Part mainly have the gases such as ammonia, hydrogen, nitrogen, methane, argon, the composition of synthesizing methanol and ammonia and methanol integrated production device periodic off-gases mainly have methanol,
The gases such as hydrogen, nitrogen, methane, argon；The recovery comprehensive utilization of periodic off-gases, many kind and upright men did many effort, achieved good
Good effect.General producer carries out after reclaiming periodic off-gases separating obtaining ammonia (or methanol), hydrogen, returns to synthesize ammonia (or synthesis first
Alcohol) system or produce other products, residual gas discharged in burning；Also there is part producer that argon has been carried out further recovery, surplus
Residual air body also discharged in burning.
Rich in methane gas in the gas burned；That is the methane synthesizing ammonia relief gas is to be incinerated,
Although the methane in periodic off-gases is incinerated and obtains calorific value, inventors believe that and the most do not give full play to periodic off-gases comprehensive utilization
Value.
China's energy resources situation feature is: rich coal, oil starvation, few gas；Methane is the Main Ingredients and Appearance of natural gas, wastes methane
It is exactly to waste natural gas.Natural gas is clean energy resource, and natural gas index is by the strict control of country, and gas chemical industry's project is state
The strict project controlling development of family；So, we can utilize the methane gas in periodic off-gases to develop natural gas fine chemistry industry, builds
If synthesis hydrocyanic acid and derivant device thereof, it is achieved resource fully comprehensively utilizes.
Summary of the invention
The deficiency comprehensively utilized for periodic off-gases described above, proposes a kind of to utilize periodic off-gases to produce hydrocyanic acid derivant
Environment-friendly clean process method, both can well realize the comprehensive utilization of periodic off-gases, can be again development natural gas fine chemistry industry
Open up a new approach, it is achieved that resource makes full use of the environment-friendly clean process of Mode of Circular and produces.
It is an object of the invention to provide the environment-friendly clean process method utilizing periodic off-gases to produce hydrocyanic acid derivant, its feature
It is to utilize the periodic off-gases containing methane such as synthesis ammonia, synthesizing methanol and ammonia and methanol integrated production by separation means such as pressure-variable adsorptions, it is achieved
Ammonia (or methanol), hydrogen, nitrogen, methane separation in periodic off-gases；Ammonia (or methanol), hydrogen, nitrogen return synthesis ammonia (or synthesizing methanol) system
Making full use of, methane is used for producing hydrocyanic acid derivant, and tail gas is for the recycling of argon；Methane is used for producing hydrocyanic acid and spreads out
Biology, refers to utilize the methane gas of periodic off-gases isolated to be directly used in ammoxidation or ammonification dehydrogenation synthesis hydrocyanic acid, hydrogen cyanogen
Acid and sodium hydrate aqueous solution absorb reaction and obtain Cyanogran. for synthesizing downstream hydrocyanic acid derivant and formaldehyde and other aldehydes
Synthesis of hydroxy acetonitrile and other hydrocyanic acid derivant be used for synthesizing downstream hydrocyanic acid derivant, with water or other solvent absorption and carry
The pure high purity liquid hydrocyanic acid that obtains is for synthesizing downstream hydrocyanic acid derivant.
What the present invention provided utilizes periodic off-gases to produce the environment-friendly clean process method of hydrocyanic acid derivant, and it is embodied as step
Rapid as follows:
The first step: the recovery of all periodic off-gases containing methane gas such as synthesis ammonia, synthesizing methanol and ammonia and methanol integrated production separates, and obtains
Take relatively pure methane gas and be directly used in ammoxidation or ammonification dehydrogenation synthesis hydrocyanic acid and hydrocyanic acid downstream derivative thing thereof.
Containing gases such as ammonia, hydrogen, nitrogen, methane, argons in synthesis ammonia relief gas, set by pressure-swing absorption apparatus and other separation
Back-up is from respectively obtaining ammonia, hydrogen, nitrogen, methane gas and tail gas；Ammonia, hydrogen, nitrogen return synthesis ammonia system, methane gas
Being directly used in ammoxidation or ammonification dehydrogenation synthesis hydrocyanic acid and hydrocyanic acid downstream derivative thing thereof, tail gas is used further to the recovery of argon.
Containing gases such as methanol, hydrogen, nitrogen, methane, argons in synthesizing methanol and ammonia and methanol integrated production periodic off-gases, filled by pressure-variable adsorption
Put and other separation equipment respectively obtains methanol, hydrogen, nitrogen, methane gas and tail gas；Methanol, hydrogen, nitrogen return and close
Becoming methanol or ammonia and methanol integrated production system, methane gas is directly used in ammoxidation or ammonification dehydrogenation synthesis hydrocyanic acid and derivant, tail gas
It is used further to the recovery of argon.
For other periodic off-gases containing methane gas component (or claiming tail gas), set by pressure-swing absorption apparatus and other separation
Standby isolated methane gas, is directly used in ammoxidation or ammonification dehydrogenation synthesis hydrocyanic acid and hydrocyanic acid downstream derivative thereof by methane gas
Thing.The prescription of the methane gas being directly used in ammoxidation or ammonification dehydrogenation synthesis hydrocyanic acid is more relaxed, and prevailing quality refers to
Mark as follows: methane gas >=90.0% (volume), hydrogen≤8.0% (volume), nitrogen≤9.0% (volume).
Second step: methane gas is directly used in ammoxidation or the ammonification dehydrogenation synthesis multiple hydrocyanic acid of hydrocyanic acid resynthesis derives
Thing.Ammoxidation or ammonification dehydrogenation synthesis hydrocyanic acid reaction gas absorb reaction with sodium hydrate aqueous solution and obtain high-purity Cyanogran. and close
Become downstream hydrocyanic acid derivant and formaldehyde and other aldehydes synthesis of hydroxy acetonitrile and other hydrocyanic acid derivant and synthesize downstream hydrogen
Cyanuric acid derivatives, with water or other solvent absorption and purify obtain high purity liquid hydrocyanic acid and synthesize downstream hydrocyanic acid derivant.
Methane ammoxidation primary response equation:
CH4+NH3+3/2O2→HCN+3H2O
Methane ammonification dehydrogenation primary response equation:
CH4+NH3→HCN+3H2
1, the hydrocyanic acid during sodium hydrate aqueous solution absorbs synthesis gas, produces and obtains liquid sodium cyanide or solid sodium cyanide,
For producing Cyanogran. downstream product.
NaOH+HCN→NaCN+H2O
Hydrocyanic acid in methane gas ammoxidation or ammonification dehydrogenation synthetic reaction gas and the sodium hydroxide in absorbing liquid react raw
Becoming Cyanogran., containing free ammonia in the synthetic reaction gas that reaction obtains, this absorption process is not have warp at synthetic reaction gas
Crossing the absorption process removing the hydrocyanic acid that ammonia operation is directly carried out, its free ammonia remains in tail gas, at tail gas after absorbing reaction
Carry out the recycling of free ammonia during process again, processed by ammonia separation retracting device and obtain being used directly for ammoxidation or ammonia
The raw material ammonia of fluidized dehydrogenation synthetic reaction, it is achieved that the recycling of free ammonia produces with the cleaning of Cyanogran..
Above-mentioned absorption reaction has obtained sodium cyanide solution, obtains liquid sodium cyanide product by cooling allotment；By dense
Contracting, crystallize, be centrifuged, be dried to obtain Cyanogran. solid product, crystalline mother solution is directly or purification rear enclosure is used sodium hydroxide and absorbed anti-
Answer in liquid.
2, formalin or other organic aldehydes absorb the hydrocyanic acid in synthesis gas, and reaction obtains hydroxyl acetonitrile aqueous solution
Or other hydrocyanic acid derivant, it is used for producing multiple hydrocyanic acid derivant downstream product.
CH2O+HCN→HOCH2CN
Containing a certain amount of free ammonia in the reaction gas of methane gas ammoxidation or ammonification dehydrogenation synthesis hydrocyanic acid, we use
Combine except the technical matters of ammonia realizes the recycling of ammonia, it is achieved cleaning produces.
3, by the hydrocyanic acid in water or other solvent absorption synthesis gas, purified by modes such as parsing or rectification and obtain liquid
Body hydrocyanic acid, liquid hydrocyanic acid is used for synthesizing hydrocyanic acid derivant and downstream product.
Containing a certain amount of free ammonia in the reaction gas of methane gas ammoxidation or ammonification dehydrogenation synthesis hydrocyanic acid, we use
Combine except the technical matters of ammonia realizes the recycling of ammonia, it is achieved cleaning produces.
3rd step: the tail gas absorbed after reclaiming with free ammonia by hydrocyanic acid uses water or sodium hydrate aqueous solution or first again
Aldehyde aqueous solution purifies and absorbs, and hydrocyanic acid remaining in tail gas is purified gathers in the crops a small amount of hydrocyanic acid aqueous solution or Cyanogran. is thick simultaneously
Product aqueous solution or the formalin of hydroxyl acetonitrile, the tail gas boiler of the tail gas after purification burns.
NaOH+HCN→NaCN+H2O
CH2O+HCN→HOCH2CN
Although the amount of free hydrogen cyanic acid remaining in tail gas system is very limited, but owing to hydrocyanic acid belongs to extremely toxic substance；I
Tail gas must be carried out purified treatment, can also gather in the crops simultaneously a small amount of hydrocyanic acid aqueous solution or Cyanogran. crude product aqueous solution or
The formalin of hydroxyl acetonitrile；The hydrocyanic acid aqueous solution obtained directly overlaps to be used in hydrocyanic acid absorption water or absorbing by liquid caustic soda liquid
In, the Cyanogran. crude product aqueous solution that obtains directly overlap the formalin of hydroxyl acetonitrile used in absorbing by liquid caustic soda liquid, obtain
Directly set is used in formaldehyde absorbent, and the tail gas after purified treatment send tail gas burning boiler to burn again.
By as above three steps, complete that the present invention provides to utilize periodic off-gases to produce the environmental protection of hydrocyanic acid derivant clear
Clean process.Its step process is: carried out point by pressure-swing absorption apparatus and other separation equipment by the periodic off-gases containing methane
From obtaining ammonia (or methanol), hydrogen, nitrogen, methane gas and tail gas, ammonia (or methanol), hydrogen, nitrogen bout ammonification or synthesis first
Alcohol system makes full use of, and methane gas is used for synthesizing hydrocyanic acid reproduction hydrocyanic acid derivant, and tail gas is for the recycling of argon；
Methane gas ammoxidation or ammonification dehydrogenation synthesis hydrocyanic acid are used for synthesizing various hydrocyanic acid derivant: methane gas passes through ammoxidation or ammonia
Fluidized dehydrogenation synthesis hydrocyanic acid synthesis gas, synthesis gas and sodium hydrate aqueous solution absorb reaction and obtain Cyanogran. for synthesizing downstream hydrogen
Cyanuric acid derivatives, synthesis gas and formaldehyde and other organic aldehyde class synthesis of hydroxy acetonitrile and other hydrocyanic acid derivant are under synthesis
Trip hydrocyanic acid derivant, synthesis gas water or other solvent absorption also resolve purification and obtain liquid hydrocyanic acid for synthesizing downstream hydrogen
Cyanuric acid derivatives.
What the present invention provided utilizes synthesis ammonia relief gas to produce the environment-friendly clean process method of hydrocyanic acid derivant, it is adaptable to
The periodic off-gases containing methane relating to the process units such as all synthesis ammonia, synthesizing methanol and ammonia and methanol integrated production produces hydrocyanic acid derivant
Process；The technology of the present invention method provides and can realize synthesizing containing of the process units such as ammonia, synthesizing methanol and ammonia and methanol integrated production
The environment-protecting clean manufacturing technique method of the comprehensive utilization of resources Mode of Circular of the periodic off-gases of methane.
The technical matters that the present invention provides, has the feature that
1, the present invention utilizes periodic off-gases to produce hydrocyanic acid derivant, achieves periodic off-gases resource comprehensive profit the most up hill and dale
With, it is thus achieved that good economic benefit and social benefit, define perfect Mode of Circular, it is achieved that environment-protecting clean produces.
2, the invention provides a kind of new raw material approach of natural gas fine chemistry industry.Although the amount of periodic off-gases methane gas accounts for
The ratio of synthesis ammonia total amount is the most little, but synthesis ammonia, synthesizing methanol and the scale of ammonia and methanol integrated production and total amount are the hugest, institute
To comprehensively utilize periodic off-gases, the methane gas in periodic off-gases is used to produce hydrocyanic acid and derivant thereof by ammoxidation or ammonification dehydrogenation
The value created is considerable.
3, utilize the methane gas production hydrocyanic acid derivant in periodic off-gases, can give full play to synthesize ammonia, synthesizing methanol and
The comprehensive advantage of ammonia and methanol integrated production manufacturer, it is possible to use synthesis ammonia, the multiple former material of synthesizing methanol and ammonia and methanol integrated production manufacturer
The supply advantage of material, forms Fine Chemical Industry chain, opens one for synthesis ammonia, synthesizing methanol and ammonia and methanol integrated production manufacturer
New industry channel.
4, by the separation to periodic off-gases, especially after separation of methane gas, in tail gas, the content of argon has reached
To a certain degree, the best condition is also provided for the recovery of argon in tail gas；In periodic off-gases, the recovery of argon is also for closing
Ammonification, synthesizing methanol and ammonia and methanol integrated production manufacturer provide another extra earning channel that can't neglect.
5, the methane gas using periodic off-gases separating-purifying to obtain, is preferable ammoxidation or ammonification dehydrogenation synthesis hydrocyanic acid
Raw material, than common natural gas more quality-advantage；Synthesis ammonia, synthesizing methanol and ammonia and methanol integrated production unstripped gas are by fine desulfurization
Journey, periodic off-gases almost no longer contains element sulphur, so the methane gas of isolated contains element sulphur the most hardly；?
During ammoxidation or ammonification dehydrogenation synthesis hydrocyanic acid, the catalyst noble metal platinum of employing is highstrung to element sulphur, institute
With, utilize the methane gas that periodic off-gases separates use ammoxidation or ammonification dehydrogenation synthesis hydrocyanic acid technique produce hydrocyanic acid and
Derivant can extend life-span 4-8 times of catalyst, correspondingly can realize time lengthening 4-8 times of driving continuously, highly effective
Ground improves utilization rate of equipment and installations, improves product yield, reduction energy consumption, saving production cost, has fully demonstrated the work that the present invention provides
The practicality of technology.
Accompanying drawing explanation
Figure of description is that the periodic off-gases that utilizes that the present invention relates to produces the environment-friendly clean process side of hydrocyanic acid derivant
Method schematic flow sheet.
Detailed description of the invention
Carry out illustrating in greater detail the present invention below by embodiment, but the scope of the present invention should not be limited by the examples
(component ratio refers both to volume basis ratio).
Embodiment 1: synthesis ammonia relief gas is separated by pressure-variable adsorption and other auxiliary separating device, respectively obtains
H2、NH3、N2、CH4And tail gas；H2、NH3、N2Respectively enteing synthesis ammonia system to recycle, tail gas is used for reclaiming Ar, CH4For pacifying
Family name's method ammoxidation synthesis hydrocyanic acid.
Periodic off-gases isolated CH4The component of (methane gas):
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | CH4 | 96.520 | 6 | N2 | 2.328 |
| 2 | H2 | 0.978 | 7 | CO2 | 0.013 |
| 3 | H2O | 0.112 | 8 | CO | 0.005 |
| 4 | NH3 | 0.013 | 9 | Ar | 0.016 |
| 5 | O2 | 0.011 | 10 | Other | 0.004 |
Utilize above-mentioned synthesis ammonia relief gas isolated CH4(methane gas) is closed by iS-One method ammoxidation synthetic reaction
Becoming gas, synthesis gas composition is as follows:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 8.092 | 6 | N2 | 54.328 |
| 2 | NH3 | 1.508 | 7 | CO2 | 0.503 |
| 3 | H2O | 25.513 | 8 | CO | 4.705 |
| 4 | CH4 | 0.462 | 9 | H2 | 4.765 |
| 5 | O2 | 0.020 | 10 | Other | 0.104 |
Synthesis gas is obtaining high-purity Cyanogran. water without except ammonia process is the most directly absorbed reaction by sodium hydrate aqueous solution
Solution, free ammonia remains in tail gas；Sodium cyanide solution quality table is as follows:
| Outward appearance | Cyanogran. (%) | CO3 2- | NH3 + | Other |
| Water white transparency | 30.78 | 0.021 | 0.012 | Water, trace impurity |
High purity liquid Cyanogran. product is obtained by cooling allotment；High-purity sodium cyanide solution is by concentrating, crystallize, being centrifuged
Isolated high purity solid Cyanogran. product；Solid sodium cyanide product quality is as follows:
| Outward appearance | Cyanogran. (%) | CO3 2- | NH3 + | Other |
| Water white transparency | 99.58 | 0.068 | 0.008 | Water, trace impurity |
Tailgas component such as following table:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 0.2246 | 6 | N2 | 60.8716 |
| 2 | NH3 | 1.6818 | 7 | CO2 | 0.5631 |
| 3 | H2O | 25.6069 | 8 | CO | 5.2714 |
| 4 | CH4 | 0.5181 | 9 | H2 | 5.3388 |
| 5 | O2 | 0.0225 | 10 | Other | 0.0012 |
Tail gas carries out the recovery of ammonia, uses phosphoric acid or ammonium dihydrogen phosphate as absorbing carrier；Reclaim the tail gas composition after ammonia
Such as following table:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 0.2655 | 6 | N2 | 74.7016 |
| 2 | NH3 | 0.0679 | 7 | CO2 | 0.6910 |
| 3 | H2O | 10.4429 | 8 | CO | 6.4691 |
| 4 | CH4 | 0.6358 | 9 | H2 | 6.5518 |
| 5 | O2 | 0.0276 | 10 | Other | 0.1468 |
Ammonium dihydrogen phosphate absorbing ammonia is converted into ammonium hydrogen phosphate solution, by resolving the recovery with ammonia；Parse
Ammonium dihydrogen phosphate is cycled to used in the absorption of ammonia, reclaims ammonia and achieves the recycling of ammonia for ammoxidation raw material.
Tail gas after recovery ammonia is again by desalted water absorption cleaning, and hydrocyanic acid remaining in tail gas is purified to be gathered in the crops simultaneously
A small amount of hydrocyanic acid aqueous solution；Hydrocyanic acid aqueous solution quality is as follows:
| Hydrocyanic acid (%) | CO3 2-(%) | NH3 +(%) | Other |
| 2.78 | 0.78 | 0.58 | Water, trace impurity |
Hydrocyanic acid aqueous solution set is used in sodium hydroxide absorbing liquid；The component of cleaning of off-gas such as following table:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 0.0058 | 6 | N2 | 80.1532 |
| 2 | NH3 | 0.0012 | 7 | CO2 | 0.7414 |
| 3 | H2O | 4.2440 | 8 | CO | 6.9477 |
| 4 | CH4 | 0.6828 | 9 | H2 | 7.0366 |
| 5 | O2 | 0.0296 | 10 | Other | 0.1577 |
Tail gas after purification tail gas boiler burns.
Embodiment 2: with embodiment 1, utilizes above-mentioned synthesis ammonia relief gas isolated CH4(methane gas) passes through iS-One method ammonia
Oxidative synthesis reaction obtains synthesis gas；Reacting synthesis gas is by combining except ammonia obtains without ammonia or the reacting synthesis gas containing constant ammonia
Body；Obtain high purity hydroxyl acetonitrile solution except the synthesis gas formalin after ammonia absorbs, be used for synthesizing High Purity Hydrogen cyanic acid and derive
Thing.
Synthesis gas component such as following table:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 8.092 | 6 | N2 | 54.328 |
| 2 | NH3 | 1.508 | 7 | CO2 | 0.503 |
| 3 | H2O | 25.513 | 8 | CO | 4.705 |
| 4 | CH4 | 0.462 | 9 | H2 | 4.765 |
| 5 | O2 | 0.020 | 10 | Other | 0.104 |
Synthesis gas by primary realize the recycling of free ammonia except ammonia after obtain primary except ammonia synthesis gas, primary except ammino
The component such as following table of one-tenth gas:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 8.9855 | 6 | N2 | 60.8716 |
| 2 | NH3 | 0.0679 | 7 | CO2 | 0.5631 |
| 3 | H2O | 18.2415 | 8 | CO | 5.714 |
| 4 | CH4 | 0.5181 | 9 | H2 | 5.3388 |
| 5 | O2 | 0.0225 | 10 | Other | 0.1196 |
Ammonium dihydrogen phosphate absorbing ammonia is converted into ammonium hydrogen phosphate solution, by resolving the recovery with ammonia；Parse
Ammonium dihydrogen phosphate is cycled to used in the absorption of ammonia, reclaims ammonia for ammoxidation raw material；The primary recovery profit achieving ammonia except ammonia
With.
Primary sulfuric acid absorption of passing through again except ammonia synthesis gas, finely except ammonia, obtains producing ammonium sulfate byproduct；Finely except ammonia synthesis gas
Component such as following table:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 9.1558 | 6 | N2 | 62.1532 |
| 2 | NH3 | 0.0012 | 7 | CO2 | 0.5853 |
| 3 | H2O | 16.6567 | 8 | CO | 5.3628 |
| 4 | CH4 | 0.5225 | 9 | H2 | 5.4168 |
| 5 | O2 | 0.0231 | 10 | Other | 0.1226 |
The fine ammonia that removes obtains ammonium sulfate, and the purified process of ammonium sulfate condensing crystallizing obtain ammonium sulfate by-product
Product.
Finely obtaining hydroxyl acetonitrile aqueous solution except the synthesis gas formalin after ammonia absorbs, hydroxyl acetonitrile aqueous solution is used for
The production of downstream product；Tail gas send tail gas incinerator to burn.
The composition obtaining hydroxyl acetonitrile aqueous solution is as follows:
| Hydroxyacetonitrile (%) | Free formaldehyde (%) | Free CN-(%) | Other |
| 45.18 | 0.08 | 0.02 | Water, trace impurity |
Embodiment 3: with embodiment 2, utilizes above-mentioned synthesis ammonia relief gas isolated CH4(methane gas) passes through iS-One method ammonia
Oxidative synthesis reaction obtains synthesis gas；Reacting synthesis gas is by combining except ammonia obtains without ammonia or the reacting synthesis gas containing constant ammonia
Body；Hydrocyanic acid aqueous solution is obtained except the synthesis gas deionized water after ammonia absorbs, by being refining to obtain high purity liquid hydrocyanic acid,
High purity liquid hydrocyanic acid is for the synthesis of hydrocyanic acid derivant；Absorbing tail gas send tail gas incinerator to burn.Obtain high purity liquid
The quality of hydrocyanic acid is as follows:
| Hydrocyanic acid (%) | CO3 2-(%) | NH3 +(%) | Other |
| 99.78 | - | - | Water, trace impurity |
Embodiment 4: synthesizing methanol periodic off-gases is separated by pressure-variable adsorption and other auxiliary separating device, respectively obtains
H2、CH3OH、N2、CH4And tail gas；H2、CH3OH、N2Respectively enteing methanol synthetic system to recycle, tail gas is used for reclaiming Ar, CH4
Hydrocyanic acid is synthesized for iS-One method ammoxidation.
Periodic off-gases isolated CH4The component of (methane gas):
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | CH4 | 96.491 | 6 | N2 | 2.341 |
| 2 | H2 | 0.987 | 7 | CO2 | 0.014 |
| 3 | H2O | 0.114 | 8 | CO | 0.005 |
| 4 | CH3OH | 0.018 | 9 | Ar | 0.018 |
| 5 | O2 | 0.008 | 10 | Other | 0.004 |
Utilize above-mentioned synthesizing methanol periodic off-gases isolated CH4(methane gas) is obtained by iS-One method ammoxidation synthetic reaction
Synthesis gas, synthesis gas composition is as follows:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 8.287 | 6 | N2 | 54.446 |
| 2 | NH3 | 1.502 | 7 | CO2 | 0.498 |
| 3 | H2O | 25.442 | 8 | CO | 4.538 |
| 4 | CH4 | 0.451 | 9 | H2 | 4.698 |
| 5 | O2 | 0.019 | 10 | Other | 0.119 |
Synthesis gas is obtaining high-purity Cyanogran. water without except ammonia process is the most directly absorbed reaction by sodium hydrate aqueous solution
Solution, free ammonia remains in tail gas；Obtain sodium cyanide solution quality as follows:
| Outward appearance | Cyanogran. (%) | CO3 2- | NH3 + | Other |
| Water white transparency | 30.66 | 0.020 | 0.011 | Water, trace impurity |
High purity liquid Cyanogran. product is obtained by cooling allotment；High-purity sodium cyanide solution is by concentrating, crystallize, being centrifuged
Isolated high purity solid Cyanogran. product；Obtain solid sodium cyanide product quality as follows:
| Outward appearance | Cyanogran. (%) | CO3 2- | NH3 + | Other |
| Water white transparency | 99.61 | 0.064 | 0.008 | Water, trace impurity |
Tailgas component such as following table:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 0.2251 | 6 | N2 | 60.8721 |
| 2 | NH3 | 1.6815 | 7 | CO2 | 0.5637 |
| 3 | H2O | 25.5074 | 8 | CO | 5.2722 |
| 4 | CH4 | 0.5174 | 9 | H2 | 5.3369 |
| 5 | O2 | 0.0226 | 10 | Other | 0.0011 |
Tail gas carries out the recovery of ammonia, uses phosphoric acid or ammonium dihydrogen phosphate as absorbing carrier；Reclaim the tail gas composition after ammonia
Such as following table:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 0.2648 | 6 | N2 | 74.7012 |
| 2 | NH3 | 0.0682 | 7 | CO2 | 0.6913 |
| 3 | H2O | 10.4432 | 8 | CO | 6.4718 |
| 4 | CH4 | 0.6361 | 9 | H2 | 6.5511 |
| 5 | O2 | 0.0274 | 10 | Other | 0.1449 |
Ammonium dihydrogen phosphate absorbing ammonia is converted into ammonium hydrogen phosphate solution, by resolving the recovery with ammonia；Parse
Ammonium dihydrogen phosphate is cycled to used in the absorption of ammonia, reclaims ammonia and achieves the recycling of ammonia for ammoxidation raw material.
Tail gas after recovery ammonia is again by desalted water absorption cleaning, and hydrocyanic acid remaining in tail gas is purified to be gathered in the crops simultaneously
A small amount of hydrocyanic acid aqueous solution；Hydrocyanic acid aqueous solution composition is as follows:
| Hydrocyanic acid (%) | CO3 2-(%) | NH3 +(%) | Other |
| 2.69 | 0.77 | 0.56 | Water, trace impurity |
Hydrocyanic acid aqueous solution set is used in sodium hydroxide absorbing liquid；The component of cleaning of off-gas such as following table:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 0.0056 | 6 | N2 | 80.1498 |
| 2 | NH3 | 0.0011 | 7 | CO2 | 0.7426 |
| 3 | H2O | 4.2438 | 8 | CO | 6.9486 |
| 4 | CH4 | 0.6832 | 9 | H2 | 7.0379 |
| 5 | O2 | 0.0301 | 10 | Other | 0.1573 |
Tail gas after purification tail gas boiler burns.
Embodiment 5: with embodiment 4, utilizes above-mentioned synthesizing methanol periodic off-gases isolated CH4(methane gas) passes through iS-One method
Ammoxidation synthetic reaction obtains synthesis gas；Reacting synthesis gas is by combining except ammonia obtains without ammonia or being synthesized containing constant ammonia
Gas；Obtain high purity hydroxyl acetonitrile solution except the synthesis gas formalin after ammonia absorbs, be used for synthesizing High Purity Hydrogen cyanic acid and spread out
Biological.
Synthesis gas component such as following table:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 8.287 | 6 | N2 | 54.446 |
| 2 | NH3 | 1.502 | 7 | CO2 | 0.498 |
| 3 | H2O | 25.442 | 8 | CO | 4.538 |
| 4 | CH4 | 0.451 | 9 | H2 | 4.698 |
| 5 | O2 | 0.019 | 10 | Other | 0.119 |
Synthesis gas by primary realize the recycling of free ammonia except ammonia after obtain primary except ammonia synthesis gas, primary except ammino
The component such as following table of one-tenth gas:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 8.936 | 6 | N2 | 60.658 |
| 2 | NH3 | 0.712 | 7 | CO2 | 0.564 |
| 3 | H2O | 17.881 | 8 | CO | 5.248 |
| 4 | CH4 | 0.523 | 9 | H2 | 5.331 |
| 5 | O2 | 0.025 | 10 | Other | 0.122 |
Ammonium dihydrogen phosphate absorbing ammonia is converted into ammonium hydrogen phosphate solution, by resolving the recovery with ammonia；Parse
Ammonium dihydrogen phosphate is cycled to used in the absorption of ammonia, reclaims ammonia for ammoxidation raw material；The primary recovery profit achieving ammonia except ammonia
With.
Primary sulfuric acid absorption of passing through again except ammonia synthesis gas, finely except ammonia, obtains producing ammonium sulfate byproduct；Finely except ammonia synthesis gas
Component such as following table:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 9.1561 | 6 | N2 | 62.1440 |
| 2 | NH3 | 0.0011 | 7 | CO2 | 0.5854 |
| 3 | H2O | 16.6648 | 8 | CO | 5.3632 |
| 4 | CH4 | 0.5226 | 9 | H2 | 5.4171 |
| 5 | O2 | 0.0232 | 10 | Other | 0.1225 |
The fine ammonia that removes obtains ammonium sulfate, and the purified process of ammonium sulfate condensing crystallizing obtain ammonium sulfate by-product
Product.
Finely obtaining hydroxyl acetonitrile aqueous solution except the synthesis gas formalin after ammonia absorbs, hydroxyl acetonitrile aqueous solution is used for
The production of downstream product；Tail gas send tail gas incinerator to burn.
The composition obtaining hydroxyl acetonitrile aqueous solution is as follows:
| Hydroxyacetonitrile (%) | Free formaldehyde (%) | Free CN-(%) | Other |
| 45.21 | 0.08 | 0.02 | Water, trace impurity |
Embodiment 6: with embodiment 5, utilizes above-mentioned synthesizing methanol periodic off-gases isolated CH4(methane gas) passes through iS-One method
Ammoxidation synthetic reaction obtains synthesis gas；Reacting synthesis gas is by combining except ammonia obtains without ammonia or being synthesized containing constant ammonia
Gas；Hydrocyanic acid aqueous solution is obtained, by being refining to obtain high purity liquid hydrogen cyanogen except the synthesis gas deionized water after ammonia absorbs
Acid, high purity liquid hydrocyanic acid is for the synthesis of hydrocyanic acid derivant；Absorbing tail gas send tail gas incinerator to burn.Obtain high-purity fluid
The quality of body hydrocyanic acid is as follows:
| Hydrocyanic acid (%) | CO3 2-(%) | NH3 +(%) | Other |
| 99.81 | - | - | Water, trace impurity |
Embodiment 7: ammonia and methanol integrated production periodic off-gases is separated by pressure-variable adsorption and other auxiliary separating device, respectively obtains
H2、CH3OH、N2、CH4And tail gas；H2、CH3OH、N2Respectively enteing synthesis ammonia system to recycle, tail gas is used for reclaiming Ar, CH4With
Hydrocyanic acid is synthesized in iS-One method ammoxidation.
Periodic off-gases isolated CH4The component of (methane gas):
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | CH4 | 96.493 | 6 | N2 | 2.346 |
| 2 | H2 | 0.981 | 7 | CO2 | 0.013 |
| 3 | H2O | 0.116 | 8 | CO | 0.005 |
| 4 | CH3OH | 0.013 | 9 | Ar | 0.018 |
| 5 | O2 | 0.011 | 10 | Other | 0.004 |
Utilize above-mentioned periodic off-gases isolated CH4(methane gas) obtains synthesis gas by iS-One method ammoxidation synthetic reaction,
Synthesis gas composition is as follows:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 8.106 | 6 | N2 | 54.335 |
| 2 | NH3 | 1.502 | 7 | CO2 | 0.502 |
| 3 | H2O | 25.511 | 8 | CO | 4.702 |
| 4 | CH4 | 0.459 | 9 | H2 | 4.762 |
| 5 | O2 | 0.019 | 10 | Other | 0.102 |
Synthesis gas is obtaining high-purity Cyanogran. water without except ammonia process is the most directly absorbed reaction by sodium hydrate aqueous solution
Solution, free ammonia remains in tail gas；Sodium cyanide solution quality is as follows:
| Outward appearance | Cyanogran. (%) | CO3 2- | NH3 + | Other |
| Water white transparency | 30.59 | 0.020 | 0.011 | Water, trace impurity |
High purity liquid Cyanogran. product is obtained by cooling allotment；High-purity sodium cyanide solution is by concentrating, crystallize, being centrifuged
Isolated high purity solid Cyanogran. product；Solid sodium cyanide product quality is as follows:
| Outward appearance | Cyanogran. (%) | CO3 2- | NH3 + | Other |
| Water white transparency | 99.62 | 0.066 | 0.008 | Water, trace impurity |
Tailgas component such as following table:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 0.2250 | 6 | N2 | 60.7728 |
| 2 | NH3 | 1.6821 | 7 | CO2 | 0.5626 |
| 3 | H2O | 25.6073 | 8 | CO | 5.2709 |
| 4 | CH4 | 0.5178 | 9 | H2 | 5.3379 |
| 5 | O2 | 0.0224 | 10 | Other | 0.0012 |
Tail gas carries out the recovery of ammonia, uses phosphoric acid or ammonium dihydrogen phosphate as absorbing carrier；Reclaim the tail gas composition after ammonia
Such as following table:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 0.2646 | 6 | N2 | 74.7014 |
| 2 | NH3 | 0.0680 | 7 | CO2 | 0.6912 |
| 3 | H2O | 10.4441 | 8 | CO | 6.4687 |
| 4 | CH4 | 0.6352 | 9 | H2 | 6.5522 |
| 5 | O2 | 0.0274 | 10 | Other | 0.1472 |
Ammonium dihydrogen phosphate absorbing ammonia is converted into ammonium hydrogen phosphate solution, by resolving the recovery with ammonia；Parse
Ammonium dihydrogen phosphate is cycled to used in the absorption of ammonia, reclaims ammonia and achieves the recycling of ammonia for ammoxidation raw material.Recovery ammonia
After tail gas again by desalted water absorption cleaning, hydrocyanic acid remaining in tail gas is purified that to gather in the crops a small amount of hydrocyanic acid water-soluble simultaneously
Liquid；Hydrocyanic acid aqueous solution composition is as follows:
| Hydrocyanic acid (%) | CO3 2-(%) | NH3 +(%) | Other |
| 2.59 | 0.72 | 0.55 | Water, trace impurity |
Hydrocyanic acid aqueous solution set is used in sodium hydroxide absorbing liquid；The component of cleaning of off-gas such as following table:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 0.0054 | 6 | N2 | 80.1545 |
| 2 | NH3 | 0.0013 | 7 | CO2 | 0.7412 |
| 3 | H2O | 4.2444 | 8 | CO | 6.9475 |
| 4 | CH4 | 0.6833 | 9 | H2 | 7.0359 |
| 5 | O2 | 0.0294 | 10 | Other | 0.1571 |
Tail gas after purification tail gas boiler burns.
Embodiment 8: with embodiment 7, utilizes above-mentioned ammonia and methanol integrated production periodic off-gases isolated CH4(methane gas) passes through iS-One method
Ammoxidation synthetic reaction obtains synthesis gas；Reacting synthesis gas is by combining except ammonia obtains without ammonia or being synthesized containing constant ammonia
Gas；Obtain high purity hydroxyl acetonitrile solution except the synthesis gas formalin after ammonia absorbs, be used for synthesizing High Purity Hydrogen cyanic acid and spread out
Biological.Synthesis gas component such as following table:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 8.101 | 6 | N2 | 54.319 |
| 2 | NH3 | 1.507 | 7 | CO2 | 0.504 |
| 3 | H2O | 25.507 | 8 | CO | 4.709 |
| 4 | CH4 | 0.463 | 9 | H2 | 4.768 |
| 5 | O2 | 0.019 | 10 | Other | 0.103 |
Synthesis gas by primary realize the recycling of free ammonia except ammonia after obtain primary except ammonia synthesis gas, primary except ammino
The component such as following table of one-tenth gas:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 8.9858 | 6 | N2 | 60.8722 |
| 2 | NH3 | 0.0678 | 7 | CO2 | 0.5632 |
| 3 | H2O | 18.2413 | 8 | CO | 5.2717 |
| 4 | CH4 | 0.5180 | 9 | H2 | 5.3385 |
| 5 | O2 | 0.0221 | 10 | Other | 0.1194 |
Ammonium dihydrogen phosphate absorbing ammonia is converted into ammonium hydrogen phosphate solution, by resolving the recovery with ammonia；Parse
Ammonium dihydrogen phosphate is cycled to used in the absorption of ammonia, reclaims ammonia for ammoxidation raw material；The primary recovery profit achieving ammonia except ammonia
With.
Primary sulfuric acid absorption of passing through again except ammonia synthesis gas, finely except ammonia, obtains producing ammonium sulfate byproduct；Finely except ammonia synthesis gas
Component such as following table:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 9.1564 | 6 | N2 | 62.1518 |
| 2 | NH3 | 0.0011 | 7 | CO2 | 0.5850 |
| 3 | H2O | 16.6582 | 8 | CO | 5.3626 |
| 4 | CH4 | 0.5222 | 9 | H2 | 5.4174 |
| 5 | O2 | 0.0230 | 10 | Other | 0.1223 |
The fine ammonia that removes obtains ammonium sulfate, and the purified process of ammonium sulfate condensing crystallizing obtain ammonium sulfate by-product
Product.
Finely obtaining hydroxyl acetonitrile aqueous solution except the synthesis gas formalin after ammonia absorbs, hydroxyl acetonitrile aqueous solution is used for
The production of downstream product；Tail gas send tail gas incinerator to burn.The composition obtaining hydroxyl acetonitrile aqueous solution is as follows:
| Hydroxyacetonitrile (%) | Free formaldehyde (%) | Free CN-(%) | Other |
| 45.26 | 0.08 | 0.02 | Water, trace impurity |
Embodiment 9: with embodiment 8, utilizes above-mentioned ammonia and methanol integrated production periodic off-gases isolated CH4(methane gas) passes through iS-One method
Ammoxidation synthetic reaction obtains synthesis gas；Reacting synthesis gas is by combining except ammonia obtains without ammonia or being synthesized containing constant ammonia
Gas；Hydrocyanic acid aqueous solution is obtained, by being refining to obtain high purity liquid hydrogen cyanogen except the synthesis gas deionized water after ammonia absorbs
Acid, high purity liquid hydrocyanic acid is for the synthesis of hydrocyanic acid derivant；Absorbing tail gas send tail gas incinerator to burn.Obtain high-purity fluid
The quality of body hydrocyanic acid is as follows:
| Hydrocyanic acid (%) | CO3 2-(%) | NH3 +(%) | Other |
| 99.80 | - | - | Water, trace impurity |
Claims (1)
1. utilize periodic off-gases to produce an environment-friendly clean process method for hydrocyanic acid derivant, it is characterized in that utilizing synthesis ammonia, conjunction
Become the periodic off-gases containing methane such as methanol and ammonia and methanol integrated production by separation means such as pressure-variable adsorptions, it is achieved ammonia or first in periodic off-gases
The separation of alcohol, hydrogen, nitrogen, methane etc.；Ammonia or methanol, hydrogen, nitrogen return synthesis ammonia or methanol synthetic system make full use of, and methane is used for
Produce hydrocyanic acid derivant: the methane gas of periodic off-gases isolated is directly used in ammoxidation or ammonification dehydrogenation synthesis hydrocyanic acid；
The prescription of methane gas is more relaxed: by volume, methane gas >=90.0%, hydrogen≤8.0%, nitrogen≤9.0%；Hydrogen cyanogen
Acid and sodium hydrate aqueous solution absorb reaction and obtain Cyanogran. for synthesizing downstream hydrocyanic acid derivant and formaldehyde and other aldehydes
Synthesis of hydroxy acetonitrile and other hydrocyanic acid derivant be used for synthesizing downstream hydrocyanic acid derivant, with water or other solvent absorption and carry
Pure obtain high purity liquid hydrocyanic acid and for synthesizing downstream hydrocyanic acid derivant；Tail gas is for the recycling of argon.
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