CN113402435A - Method for preparing caprolactam by catalyzing cyclohexanone oxime with nicotinic acid in refining of smelting tail gas - Google Patents
Method for preparing caprolactam by catalyzing cyclohexanone oxime with nicotinic acid in refining of smelting tail gas Download PDFInfo
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- CN113402435A CN113402435A CN202110589579.XA CN202110589579A CN113402435A CN 113402435 A CN113402435 A CN 113402435A CN 202110589579 A CN202110589579 A CN 202110589579A CN 113402435 A CN113402435 A CN 113402435A
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- tail gas
- smelting tail
- sulfuric acid
- nickel smelting
- oleum
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- 238000000034 method Methods 0.000 title claims abstract description 107
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 238000003723 Smelting Methods 0.000 title claims abstract description 96
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 title claims abstract description 88
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229960003512 nicotinic acid Drugs 0.000 title claims abstract description 19
- 235000001968 nicotinic acid Nutrition 0.000 title claims abstract description 19
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 19
- 238000007670 refining Methods 0.000 title claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 95
- 230000008569 process Effects 0.000 claims abstract description 72
- 238000010521 absorption reaction Methods 0.000 claims abstract description 58
- 238000001035 drying Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003546 flue gas Substances 0.000 claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 21
- 238000000746 purification Methods 0.000 claims abstract description 21
- 238000006237 Beckmann rearrangement reaction Methods 0.000 claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 154
- 229910052759 nickel Inorganic materials 0.000 claims description 77
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 57
- 239000000428 dust Substances 0.000 claims description 42
- 238000007599 discharging Methods 0.000 claims description 37
- 238000005406 washing Methods 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 238000000108 ultra-filtration Methods 0.000 claims description 18
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 10
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 7
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052785 arsenic Inorganic materials 0.000 claims description 7
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 7
- 229910001424 calcium ion Inorganic materials 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 7
- 239000003595 mist Substances 0.000 claims description 7
- 238000006462 rearrangement reaction Methods 0.000 claims description 7
- 230000009466 transformation Effects 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000013589 supplement Substances 0.000 claims description 2
- 230000002939 deleterious effect Effects 0.000 claims 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 3
- 229910052683 pyrite Inorganic materials 0.000 description 3
- 239000011028 pyrite Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- AXTGDCSMTYGJND-UHFFFAOYSA-N 1-dodecylazepan-2-one Chemical compound CCCCCCCCCCCCN1CCCCCC1=O AXTGDCSMTYGJND-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 241000695274 Processa Species 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 229940127218 antiplatelet drug Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229960003639 laurocapram Drugs 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000106 platelet aggregation inhibitor Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/02—Preparation of lactams
- C07D201/04—Preparation of lactams from or via oximes by Beckmann rearrangement
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/56—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D223/08—Oxygen atoms
- C07D223/10—Oxygen atoms attached in position 2
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
The application provides a method for preparing caprolactam by catalyzing cyclohexanone oxime with nicotinic acid in refining of smelting tail gas, through carrying out flue gas purification, drying, conversion and absorption treatment processes on the smelting tail gas, some harmful impurities (such as ash, metal impurities and the like) can be effectively removed, so that fuming sulfuric acid meeting the requirement of preparing caprolactam can be prepared, and the fuming sulfuric acid meeting the requirement catalyzes cyclohexanone oxime to carry out Beckmann rearrangement to produce caprolactam, so that the industrialization is easy to realize.
Description
Technical Field
The application relates to the technical field of caprolactam production, in particular to a method for preparing caprolactam by catalyzing cyclohexanone oxime with nicotinic acid generated by refining smelting tail gas.
Background
Caprolactam is an important organic chemical raw material, is mainly used for producing nylon-6 fiber and engineering plastics, can be used for producing antiplatelet drugs, 6-aminocaproic acid, laurocapram and the like, and has wide application. Among them, cyclohexanone oxime is a key intermediate for producing caprolactam. The cyclohexanone oxime is Beckmann rearranged to prepare caprolactam, except for a gas phase rearrangement process, most of the cyclohexanone oxime is prepared by using fuming sulfuric acid as a reaction medium. The current Beckmann rearrangement process of cyclohexanone oxime is carried out under fuming sulfuric acid prepared from elemental sulfur or pyrite and high temperature conditions.
However, the production of oleum from elemental sulfur or pyrite produces sulfuric acid, which causes environmental pollution, and thus there is an urgent need for more environmentally friendly methods for producing oleum. In order to effectively utilize the nickel smelting tail gas, fuming sulfuric acid can be prepared by the nickel smelting tail gas, but in the fuming sulfuric acid process prepared by recovering the nickel smelting tail gas, ash content and metal impurities cannot be effectively controlled, so that the prepared fuming sulfuric acid has poor quality, and the preparation process of caprolactam is influenced.
Disclosure of Invention
The application provides a method for preparing caprolactam by catalyzing cyclohexanone oxime with nicotinic acid generated in refining of smelting tail gas, which is used for solving the problem that the quality of the prepared fuming sulfuric acid is poor.
On one hand, the application provides a method for preparing caprolactam by catalyzing cyclohexanone oxime with nicotinic acid in refining of smelting tail gas, which comprises the following steps:
the flue gas purification treatment process comprises the following steps: discharging nickel smelting tail gas into a washing tower, and performing electrostatic dust removal and demisting on the nickel smelting tail gas through two-stage voltage in the washing tower to remove harmful impurities in the nickel smelting tail gas, wherein the voltage range of the two-stage electric dust remover is 45-55 KV, and the voltage of the front-stage electric dust remover in the two-stage voltage is smaller than that of the rear-stage electric dust remover;
and (3) drying treatment process: discharging the nickel smelting tail gas subjected to the flue gas purification treatment into a drying tower, spraying concentrated sulfuric acid with a first concentration into the drying tower, and absorbing water in the nickel smelting tail gas through the concentrated sulfuric acid with the first concentration in the drying tower;
and (3) transformation process: discharging the dried nickel smelting tail gas into a converter, wherein the temperature in the converter is 410-480 ℃, the pressure in the converter is 19.0-21.0Kpa, and SO in the nickel smelting tail gas is discharged into the converter2Conversion to SO3；
And (3) an absorption process: SO obtained by conversion3Discharging into an absorption tower, wherein the temperature in the absorption tower is 150-165 ℃, and the temperature in the absorption tower isConcentrated sulfuric acid with second concentration is filled in the absorption tower, and the concentrated sulfuric acid with second concentration repeatedly absorbs SO in the absorption tower3Obtaining oleum, wherein the second concentration is higher than the first concentration;
the Beckmann rearrangement reaction process: mixing the obtained oleum with cyclohexanone oxime, wherein the mass ratio of the oleum to the cyclohexanone oxime is 1.26-1.35, and the cyclohexanone oxime is subjected to Beckmann molecular rearrangement reaction in the presence of the oleum and at the temperature of 105-115 ℃ to obtain caprolactam.
In one possible implementation, the scrubber is a cyclonic spiral scrubber;
the method for carrying out electrostatic dust removal and demisting on the nickel smelting tail gas in the washing tower through two-stage voltage comprises the following steps:
and carrying out dilute sulfuric acid washing on the nickel smelting tail gas in the cyclone spiral washing tower and carrying out electrostatic dust removal and demisting on the nickel smelting tail gas through two-stage voltage.
In a possible implementation manner, the method of this embodiment further includes:
softened water is also discharged into the absorption tower to supplement the softened water in the absorption process.
In a possible implementation manner, the method of this embodiment further includes:
the softened water preparation process comprises the following steps: discharging the production water into an ultrafiltration device, and preparing the softened water by the ultrafiltration device, wherein the ultrafiltration device is used for removing and softening metal ions in the production water.
In one possible implementation, the metal ions include one or more of: calcium ions, magnesium ions.
In one possible implementation, the converter contains vanadium pentoxide;
SO in the nickel smelting tail gas under the catalytic action of the vanadium pentoxide2Conversion to SO3。
In one possible implementation, the first concentration is 93% and the second concentration is 98%.
In one possible implementation, the harmful impurities include one or more of: dust, fluorine, arsenic, acid mist.
In one possible implementation, the oleum is 104.5% oleum.
In another aspect, the present application provides a caprolactam prepared by a process as described in the above-described aspect.
The application provides a method for preparing caprolactam by catalyzing cyclohexanone oxime with nicotinic acid in refining of smelting tail gas, through the processes of flue gas purification, drying, conversion and absorption treatment, some harmful impurities (such as ash, metal impurities and the like) can be effectively removed, so that oleum which meets the requirement of preparing caprolactam can be prepared, and the oleum which meets the requirement catalyzes cyclohexanone oxime to carry out Beckmann rearrangement to produce caprolactam, and the industrialization is easy to realize. In addition, the method has controllable process key reaction and low cost, achieves the purposes of changing waste into resources, saving energy, reducing emission, reducing secondary pollution, realizing circular economy, reducing the procurement cost of the sulfuric acid of enterprises, and is worthy of market popularization.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a flowchart illustrating a method for preparing caprolactam from cyclohexanone oxime catalyzed by nicotinic acid produced by refining smelting off-gas according to an embodiment of the present application;
FIG. 2 is a schematic diagram of a system for preparing caprolactam from cyclohexanone oxime catalyzed by nicotinic acid produced by refining smelting tail gas according to an embodiment of the present application;
FIG. 3 is a flow chart of a method for preparing caprolactam from cyclohexanone oxime catalyzed by nicotinic acid produced by refining smelting off-gas according to another embodiment of the present application;
FIG. 4 is a schematic structural diagram of a system for preparing caprolactam by catalyzing cyclohexanone oxime with nicotinic acid from refining of smelting off-gas according to another embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present application, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The acid quality requirement for caprolactam production is strict, ash and metal impurities in acid have adverse effects on product quality, however, fuming sulfuric acid prepared by recovering nickel smelting tail gas under the existing conditions is poor in quality, and the ash and the metal impurities cannot be effectively controlled, so that the fuming sulfuric acid prepared by recovering nickel smelting tail gas is used for catalyzing cyclohexanone oxime to prepare caprolactam, the sulfuric acid preparation process of a nickel ore smelting plant needs to be optimized, the quality of the fuming sulfuric acid is improved, waste is changed into resources, energy is saved, emission is reduced, secondary pollution is reduced, the purpose of circular economy is realized, and the purchase cost of sulfuric acid of enterprises is reduced.
The scheme of the present application is described in detail below with specific examples.
Fig. 1 is a flowchart of a method for preparing caprolactam by catalyzing cyclohexanone oxime with smelting tail gas refining nicotinic acid, and fig. 2 is a schematic diagram of a system for preparing caprolactam by catalyzing cyclohexanone oxime with smelting tail gas refining nicotinic acid, which are provided by an embodiment of the present application, and as shown in fig. 1 and fig. 2, the method of this embodiment may include:
s101, a flue gas purification treatment process.
In this embodiment, a washing tower needs to be used in the flue gas purification treatment process, and the specific process is as follows: and discharging the nickel smelting tail gas into a washing tower, and performing electrostatic dust removal and demisting on the nickel smelting tail gas in the washing tower through a two-stage electric dust remover so as to remove harmful impurities in the nickel smelting tail gas. Specifically, the electrostatic dust removal demisting is used for removing one or more of the following nickel smelting tail gas: dust, fluorine, arsenic, acid mist.
The voltage range of the two-stage electric dust remover is 45-55 KV, and the voltage of each stage of electric dust remover in the two-stage electric dust remover is different in magnitude. Optionally, the voltage of the electric dust remover in the previous stage is lower than that of the electric dust remover in the next stage. In some cases, the voltage of the previous stage of the two-stage voltage may be greater than or equal to the voltage of the next stage of the electric precipitator.
Optionally, the scrubber is a cyclone spiral scrubber.
One possible implementation manner of S101 is as follows: and (2) carrying out dilute sulfuric acid washing on the nickel smelting tail gas in the cyclone spiral washing tower, and carrying out electrostatic dust removal and demisting on the nickel smelting tail gas through the two-stage voltage so as to remove harmful impurities (such as smoke dust, heavy metals and the like) in the nickel smelting tail gas.
Wherein, the dilute sulfuric acid refers to the aqueous solution of sulfuric acid with the solute mass fraction less than or equal to 70%.
S102, drying process.
In this embodiment, after the nickel smelting tail gas is subjected to the flue gas purification treatment, the nickel smelting tail gas subjected to the flue gas purification treatment is dried. Among them, a drying tower is required in the drying process. Specifically, the nickel smelting tail gas after the flue gas purification treatment is discharged into a drying tower. Concentrated sulfuric acid with a first concentration is sprayed in the drying tower, and water in the nickel smelting tail gas is absorbed by the concentrated sulfuric acid with the first concentration in the drying tower. Wherein, the concentrated sulfuric acid is a sulfuric acid aqueous solution with the mass fraction of more than or equal to 70 percent.
Optionally, the concentrated sulfuric acid with the first concentration is 93% concentrated sulfuric acid.
S103, a conversion process.
In this embodiment, after the nickel smelting tail gas is dried, the nickel smelting tail gas is converted. Wherein, during the transformation processA converter is required. Specifically, the nickel smelting tail gas after drying treatment is discharged into a converter. The temperature in the converter is 410-480 ℃, the pressure in the converter is 19.0-21.0Kpa, and SO in the nickel smelting tail gas is converted in the converter with the temperature and the pressure2Conversion to SO3。
Optionally, the converter in this embodiment further contains vanadium pentoxide, and under the catalytic action of the vanadium pentoxide, SO in the nickel smelting tail gas2Conversion to SO3. In the embodiment, the SO in the nickel smelting tail gas can be accelerated by the catalysis of the vanadium pentoxide2Conversion to SO3Thereby increasing SO in the nickel smelting tail gas2Conversion to SO3And further quickens the efficiency of preparing the fuming sulfuric acid by the nickel smelting tail gas.
S104, an absorption process.
In this example, SO was obtained by the above-described conversion process3Then to SO3An absorption process is performed. Wherein, an absorption tower is required in the absorption process. Specifically, SO obtained by conversion3Discharging into an absorption tower. Wherein the temperature in the absorption tower is 150-165 ℃, concentrated sulfuric acid with a second concentration is filled in the absorption tower, and SO is repeatedly absorbed by the concentrated sulfuric acid with the second concentration in the absorption tower3Fuming sulfuric acid is obtained. Optionally, the resulting oleum is 104.5% oleum. Wherein the second concentration is greater than the first concentration. Optionally, the second concentration is 98%.
S105, a Beckmann rearrangement reaction process.
In this example, after obtaining oleum, the beckmann rearrangement process was performed. The use of a reactor is required during the beckmann rearrangement reaction. Specifically, the obtained oleum is mixed with cyclohexanone oxime, the mass ratio of the oleum to the cyclohexanone oxime is 1.26-1.35, and the cyclohexanone oxime is subjected to Beckmann molecular rearrangement reaction in the presence of the oleum and at the temperature of 105-115 ℃ to obtain caprolactam.
According to the method for preparing caprolactam by catalyzing cyclohexanone oxime with nicotinic acid in refining of smelting tail gas, through the processes of flue gas purification, drying, conversion and absorption, some harmful impurities (such as ash, metal impurities and the like) can be effectively removed, so that oleum meeting the requirement of preparing caprolactam can be prepared, and the oleum meeting the requirement catalyzes cyclohexanone oxime to carry out Beckmann rearrangement to produce caprolactam, so that industrialization is easy to realize. In addition, the method has controllable process key reaction and low cost, achieves the purposes of changing waste into resources, saving energy, reducing emission, reducing secondary pollution, realizing circular economy, reducing the procurement cost of the sulfuric acid of enterprises, and is worthy of market popularization.
Fig. 3 is a flowchart of a method for preparing caprolactam by catalyzing cyclohexanone oxime with smelting off-gas refining nicotinic acid, and fig. 4 is a schematic diagram of a system for preparing caprolactam by catalyzing cyclohexanone oxime with smelting off-gas refining nicotinic acid, which are provided by another embodiment of the present application, and as shown in fig. 3 and fig. 4, the method of this embodiment may include:
s301, a flue gas purification treatment process.
S302, drying process.
S303, a conversion process.
In this embodiment, the specific implementation process of S301 to S303 may refer to the related description in the embodiment shown in fig. 1, and is not described herein again.
S304, an absorption process.
In this example, softened water was also discharged from the absorption tower used in the absorption process, SO that the SO obtained by the conversion was removed3Discharging into an absorption tower. Wherein the temperature in the absorption tower is 150-165 ℃, concentrated sulfuric acid with a second concentration is filled in the absorption tower, and SO is repeatedly absorbed by the concentrated sulfuric acid with the second concentration in the absorption tower3And supplying demineralized water to obtain oleum. Wherein, because the softened water is used in the absorption process, the impurities in the softened water are less, so that the impurities are reduced in the process of preparing the oleum, and the quality of the prepared oleum is further improved.
Optionally, the resulting oleum is 104.5% oleum. Wherein the second concentration is greater than the first concentration. Optionally, the second concentration is 98%.
Optionally, the method of this embodiment may further include S305:
s305, preparing softened water.
In this embodiment, a process of preparing softened water may be further included. The ultrafiltration equipment is needed in the process of preparing softened water. Specifically, the process water is discharged into an ultrafiltration device, and the softened water is prepared by the ultrafiltration device, wherein the ultrafiltration device is used for removing and softening metal ions in the process water. The metal ions include, for example, one or more of the following: calcium ions, magnesium ions. Thus, this embodiment enables the production of demineralized water in the course of the production of oleum.
The softened water produced in S305 may be discharged into the absorption tower in S304.
It should be noted that S305 may be executed before S304, where the execution sequence of S305 and S301 to S303 is not limited.
S306, Beckmann rearrangement reaction process.
In this embodiment, a specific implementation process of S306 may refer to related descriptions in the embodiment shown in fig. 1, and details are not described here.
According to the method for preparing caprolactam by catalyzing cyclohexanone oxime by refining smelting tail gas through nicotinic acid, through the processes of purifying, drying, converting, absorbing and preparing softened water, some harmful impurities (such as ash, metal impurities and the like) can be effectively removed, so that fuming sulfuric acid with better quality can be prepared, the cost is low, the fuming sulfuric acid meeting the requirement catalyzes cyclohexanone oxime to carry out Beckmann rearrangement to produce caprolactam, and the industrialization is easy to realize. In addition, the method has controllable process key reaction and low cost, achieves the purposes of changing waste into resources, saving energy, reducing emission, reducing secondary pollution, realizing circular economy, reducing the procurement cost of the sulfuric acid of enterprises, and is worthy of market popularization.
In an embodiment of the present application, the present application further provides oleum prepared by the methods of the above embodiments.
In another embodiment, the present application also provides caprolactam prepared by the methods of the above examples.
The following illustrates the process for preparing caprolactam:
example 1
Caprolactam is prepared by the following steps:
the flue gas purification treatment process comprises the following steps: and discharging the nickel smelting tail gas into a washing tower, wherein the nickel smelting tail gas is subjected to dilute sulfuric acid washing in the cyclone spiral washing tower and is subjected to electrostatic dust removal and demisting through a first-level electric dust remover (voltage 45KV) and another-level electric dust remover (voltage 55KV) so as to remove dust, fluorine, arsenic and acid mist in the nickel smelting tail gas.
And (3) drying treatment process: and discharging the nickel smelting tail gas subjected to the flue gas purification treatment into a drying tower, and absorbing water in the nickel smelting tail gas by 93% concentrated sulfuric acid in the drying tower.
And (3) transformation process: discharging the dried nickel smelting tail gas into a converter, wherein the temperature in the converter is 410 ℃, the pressure in the converter is 19.0Kpa, and the SO in the nickel smelting tail gas is catalyzed by the vanadium pentoxide in the converter2Conversion to SO3。
The softened water preparation process comprises the following steps: discharging the production water into an ultrafiltration device, removing and softening calcium and magnesium ions in the production water through the ultrafiltration device to prepare softened water, and discharging the softened water into an absorption tower.
And (3) an absorption process: SO obtained by conversion3Discharging into an absorption tower, wherein the temperature in the absorption tower is 150 ℃, and the 98 percent concentrated sulfuric acid in the absorption tower repeatedly absorbs SO3Oleum is obtained and SO is absorbed3The process of (3) was supplemented with demineralized water, thereby obtaining 104.5% oleum of example 1, and continuously absorbing, maintaining the concentration and continuously producing acid as mother acid.
The Beckmann rearrangement reaction process: the obtained oleum is mixed with cyclohexanone oxime with the mass ratio of 1.26, and the cyclohexanone oxime undergoes Beckmann molecular rearrangement reaction in the presence of the oleum and at the temperature of 105 ℃ to obtain the caprolactam of example 1.
Example 2
Caprolactam is prepared by the following steps:
the flue gas purification treatment process comprises the following steps: and discharging the nickel smelting tail gas into a washing tower, wherein the nickel smelting tail gas is subjected to dilute sulfuric acid washing in the cyclone spiral washing tower and is subjected to electrostatic dust removal and demisting through a first-level electric dust remover (with the voltage of 50KV) and another-level electric dust remover (with the voltage of 55KV) so as to remove dust, fluorine, arsenic and acid mist in the nickel smelting tail gas.
And (3) drying treatment process: and discharging the nickel smelting tail gas subjected to the flue gas purification treatment into a drying tower, and absorbing water in the nickel smelting tail gas by 93% concentrated sulfuric acid in the drying tower.
And (3) transformation process: discharging the dried nickel smelting tail gas into a converter, wherein the temperature in the converter is 480 ℃ and the pressure in the converter is 21.0Kpa, and the SO in the nickel smelting tail gas is catalyzed by the vanadium pentoxide in the converter2Conversion to SO3。
The softened water preparation process comprises the following steps: discharging the production water into an ultrafiltration device, removing and softening calcium and magnesium ions in the production water through the ultrafiltration device to prepare softened water, and discharging the softened water into an absorption tower.
And (3) an absorption process: SO obtained by conversion3Discharging into an absorption tower, wherein the temperature in the absorption tower is 165 ℃, and the 98 percent concentrated sulfuric acid in the absorption tower repeatedly absorbs SO3Oleum is obtained and SO is absorbed3The process of (3) was supplemented with demineralized water, thereby obtaining 104.5% oleum of example 2, and continuously absorbing, maintaining the concentration and continuously producing acid as mother acid.
The Beckmann rearrangement reaction process: the obtained oleum is mixed with cyclohexanone oxime with the mass ratio of 1.3, and the cyclohexanone oxime undergoes Beckmann molecular rearrangement reaction in the presence of the oleum and at the temperature of 115 ℃ to obtain the caprolactam of example 2.
Example 3
Caprolactam is prepared by the following steps:
the flue gas purification treatment process comprises the following steps: and discharging the nickel smelting tail gas into a washing tower, wherein the nickel smelting tail gas is subjected to dilute sulfuric acid washing in the cyclone spiral washing tower and is subjected to electrostatic dust removal and demisting through a first-level electric dust remover (with the voltage of 50KV) and another-level electric dust remover (with the voltage of 55KV) so as to remove dust, fluorine, arsenic and acid mist in the nickel smelting tail gas.
And (3) drying treatment process: and discharging the nickel smelting tail gas subjected to the flue gas purification treatment into a drying tower, and absorbing water in the nickel smelting tail gas by 93% concentrated sulfuric acid in the drying tower.
And (3) transformation process: discharging the dried nickel smelting tail gas into a converter, wherein the temperature in the converter is 450 ℃, the pressure in the converter is 20.0Kpa, and the SO in the nickel smelting tail gas is catalyzed by the vanadium pentoxide in the converter2Conversion to SO3。
The softened water preparation process comprises the following steps: discharging the production water into an ultrafiltration device, removing and softening calcium and magnesium ions in the production water through the ultrafiltration device to prepare softened water, and discharging the softened water into an absorption tower.
And (3) an absorption process: SO obtained by conversion3Discharging into an absorption tower, wherein the temperature in the absorption tower is 160 ℃, and the 98 percent concentrated sulfuric acid in the absorption tower repeatedly absorbs SO3Oleum is obtained and SO is absorbed3The process of (3) was supplemented with demineralized water, whereby 104.5% oleum of example 3 was obtained, and as mother acid, continuous absorption, concentration maintenance and continuous acid production were carried out.
The Beckmann rearrangement reaction process: the obtained oleum is mixed with cyclohexanone oxime with the mass ratio of 1.35, and the cyclohexanone oxime undergoes Beckmann molecular rearrangement reaction in the presence of the oleum and at the temperature of 115 ℃ to obtain the caprolactam of example 3.
Example 4
Caprolactam is prepared by the following steps:
the flue gas purification treatment process comprises the following steps: and discharging the nickel smelting tail gas into a washing tower, wherein the nickel smelting tail gas is subjected to dilute sulfuric acid washing in the cyclone spiral washing tower and is subjected to electrostatic dust removal and demisting through a first-level electric dust remover (with the voltage of 50KV) and another-level electric dust remover (with the voltage of 55KV) so as to remove dust, fluorine, arsenic and acid mist in the nickel smelting tail gas.
And (3) drying treatment process: discharging the nickel smelting tail gas subjected to the flue gas purification treatment into a drying tower, and absorbing water in the nickel smelting tail gas by 93% concentrated sulfuric acid in the drying tower;
and (3) transformation process: discharging the dried nickel smelting tail gas into a converter, wherein the temperature in the converter is 480 ℃ and the pressure in the converter is 19.0Kpa, and the SO in the nickel smelting tail gas is catalyzed by the vanadium pentoxide in the converter2Conversion to SO3。
The softened water preparation process comprises the following steps: discharging the production water into an ultrafiltration device, removing and softening calcium and magnesium ions in the production water through the ultrafiltration device to prepare softened water, and discharging the softened water into an absorption tower.
And (3) an absorption process: SO obtained by conversion3Discharging into an absorption tower, wherein the temperature in the absorption tower is 160 ℃, and the 98 percent concentrated sulfuric acid in the absorption tower repeatedly absorbs SO3Oleum is obtained and SO is absorbed3The process of (3) was supplemented with demineralized water, thereby obtaining 104.5% oleum of example 4, and continuously absorbing, maintaining the concentration and continuously producing acid as mother acid.
The Beckmann rearrangement reaction process: the obtained oleum is mixed with cyclohexanone oxime with the mass ratio of 1.35, and the cyclohexanone oxime undergoes Beckmann molecular rearrangement reaction in the presence of the oleum and at the temperature of 110 ℃ to obtain the caprolactam of example 4.
The present application examined the quality of the oleum obtained in examples 1 to 4 above and obtained the results shown in table one.
Watch 1
The present inventors examined the quality of caprolactam obtained in examples 1 to 4 above and obtained the results shown in Table two.
Watch two
Through the scheme of each embodiment, the application has the following beneficial effects:
(1) the environment-friendly recovered by-products are recycled;
(2) the absorption process adopts desalted water, reduces the introduction of impurities, optimizes the cross-acid process, avoids mutual pollution, reduces the impurity content of nicotinic acid and improves the quality of finished fuming sulfuric acid;
(3) the caprolactam is prepared from fuming sulfuric acid prepared from nickel smelting tail gas, so that the national capacity of sulfuric acid can be reduced, and energy conservation, emission reduction, environmental protection and national resource intensive utilization are realized.
(4) The quality of fuming sulfuric acid products is improved, the application range of the products is expanded, the fuming sulfuric acid is used for caprolactam industry, and the resource utilization rate is improved.
(5) Because the nickel smelting tail gas is used for preparing acid, the cost of sulfuric acid is far lower than that of sulfur and pyrite for preparing acid, the purposes of changing waste into resources, saving energy, reducing emission, reducing secondary pollution, realizing circular economy and reducing the purchasing cost of sulfuric acid of enterprises are achieved.
(6) The preparation method is simple in preparation process, convenient to operate and easy to realize industrialization.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art; the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Claims (9)
1. A method for preparing caprolactam by catalyzing cyclohexanone oxime with nicotinic acid in refining of smelting tail gas is characterized by comprising the following steps:
the flue gas purification treatment process comprises the following steps: discharging nickel smelting tail gas into a washing tower, and performing electrostatic dust removal and demisting on the nickel smelting tail gas in the washing tower through a two-stage electric dust remover to remove harmful impurities in the nickel smelting tail gas, wherein the voltage range of the two-stage electric dust remover is 45-55 KV, and the voltage of a front-stage electric dust remover in the two-stage voltage is smaller than that of a rear-stage electric dust remover;
and (3) drying treatment process: discharging the nickel smelting tail gas subjected to the flue gas purification treatment into a drying tower, spraying concentrated sulfuric acid with a first concentration into the drying tower, and absorbing water in the nickel smelting tail gas through the concentrated sulfuric acid with the first concentration in the drying tower;
and (3) transformation process: discharging the dried nickel smelting tail gas into a converter, wherein the temperature in the converter is 410-480 ℃, the pressure in the converter is 19.0-21.0Kpa, and SO in the nickel smelting tail gas is discharged into the converter2Conversion to SO3；
And (3) an absorption process: SO obtained by conversion3Discharging into an absorption tower, wherein the temperature in the absorption tower is 150-165 ℃, concentrated sulfuric acid with a second concentration is filled in the absorption tower, and the concentrated sulfuric acid with the second concentration is filled in the absorption towerRepeated absorption of SO by concentrated sulfuric acid3Obtaining oleum, wherein the second concentration is higher than the first concentration;
the Beckmann rearrangement reaction process: mixing the obtained oleum with cyclohexanone oxime, wherein the mass ratio of the oleum to the cyclohexanone oxime is 1.26-1.35, and the cyclohexanone oxime is subjected to Beckmann molecular rearrangement reaction in the presence of the oleum and at the temperature of 105-115 ℃ to obtain caprolactam.
2. The method of claim 1, wherein the scrubber is a cyclonic spiral scrubber;
the method for carrying out electrostatic dust removal and demisting on the nickel smelting tail gas in the washing tower through two-stage voltage comprises the following steps:
and carrying out dilute sulfuric acid washing on the nickel smelting tail gas in the cyclone spiral washing tower and carrying out electrostatic dust removal and demisting on the nickel smelting tail gas through two-stage voltage.
3. The method of claim 1, further comprising:
softened water is also discharged into the absorption tower to supplement the softened water in the absorption process.
4. The method of claim 3, further comprising:
the softened water preparation process comprises the following steps: discharging the production water into an ultrafiltration device, and preparing the softened water by the ultrafiltration device, wherein the ultrafiltration device is used for removing and softening metal ions in the production water.
5. The method of claim 4, wherein the metal ions comprise one or more of: calcium ions, magnesium ions.
6. The method of claim 1, wherein the converter contains vanadium pentoxide;
at the placeSO in the nickel smelting tail gas under the catalytic action of the vanadium pentoxide2Conversion to SO3。
7. The method of claim 1, wherein the first concentration is 93% and the second concentration is 98%.
8. The method of claim 1, wherein the deleterious impurities comprise one or more of: dust, fluorine, arsenic, acid mist.
9. A process according to any one of claims 1 to 8, wherein the oleum is 104.5% oleum.
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| CN103303878A (en) * | 2013-05-30 | 2013-09-18 | 福建省邵武市永飞化工有限公司 | Method for preparing sulfuric acid by iron pyrite |
| CN108147373A (en) * | 2017-12-28 | 2018-06-12 | 广西生富锑业科技股份有限公司 | A kind of method that flue gas during smelting prepares sulfuric acid |
| CN110615409A (en) * | 2019-09-16 | 2019-12-27 | 安徽华铂再生资源科技有限公司 | Sulfur dioxide flue gas acid making process based on smelting system |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103303878A (en) * | 2013-05-30 | 2013-09-18 | 福建省邵武市永飞化工有限公司 | Method for preparing sulfuric acid by iron pyrite |
| CN108147373A (en) * | 2017-12-28 | 2018-06-12 | 广西生富锑业科技股份有限公司 | A kind of method that flue gas during smelting prepares sulfuric acid |
| CN110615409A (en) * | 2019-09-16 | 2019-12-27 | 安徽华铂再生资源科技有限公司 | Sulfur dioxide flue gas acid making process based on smelting system |
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