CN115779626A - Method for removing residual n-butanol contained in tail gas in process of synthesizing isophorone diamino acid n-butyl ester by urea method - Google Patents
Method for removing residual n-butanol contained in tail gas in process of synthesizing isophorone diamino acid n-butyl ester by urea method Download PDFInfo
- Publication number
- CN115779626A CN115779626A CN202211208020.9A CN202211208020A CN115779626A CN 115779626 A CN115779626 A CN 115779626A CN 202211208020 A CN202211208020 A CN 202211208020A CN 115779626 A CN115779626 A CN 115779626A
- Authority
- CN
- China
- Prior art keywords
- tail gas
- butanol
- ammonia
- urea
- butyl ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 238000000034 method Methods 0.000 title claims abstract description 101
- 230000008569 process Effects 0.000 title claims abstract description 37
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000004202 carbamide Substances 0.000 title claims abstract description 28
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 16
- 239000002253 acid Substances 0.000 title claims abstract description 8
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 title claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 24
- 238000001179 sorption measurement Methods 0.000 claims abstract description 22
- 239000003463 adsorbent Substances 0.000 claims abstract description 19
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 claims abstract description 17
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000002808 molecular sieve Substances 0.000 claims abstract description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 230000009615 deamination Effects 0.000 claims description 11
- 238000006481 deamination reaction Methods 0.000 claims description 11
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000003795 desorption Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000007083 alkoxycarbonylation reaction Methods 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 5
- 239000012159 carrier gas Substances 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 abstract description 15
- 239000005058 Isophorone diisocyanate Substances 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 13
- 239000012948 isocyanate Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 150000002513 isocyanates Chemical class 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- -1 comprises MDI Chemical class 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- NMJJFJNHVMGPGM-UHFFFAOYSA-N n-butylmethanoate Natural products CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- JRQLZCFSWYQHPI-UHFFFAOYSA-N 4,5-dichloro-2-cyclohexyl-1,2-thiazol-3-one Chemical compound O=C1C(Cl)=C(Cl)SN1C1CCCCC1 JRQLZCFSWYQHPI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical group NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920003009 polyurethane dispersion Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of IPDI synthesis, and particularly discloses a method for removing residual n-butanol contained in tail gas in a process for synthesizing isophorone diamino acid n-butyl ester by a urea method, wherein the tail gas is derived from the following raw materials: tail gas containing ammonia obtained by the process for synthesizing isophorone diamino n-butyl ester by a urea method is obtained by the process for removing ammonium carbamate; the method for removing the residual n-butanol in the tail gas comprises the following steps: cooling the tail gas to 15-25 ℃, and then adsorbing n-butyl alcohol in the tail gas by using an adsorbent; the adsorbent comprises a molecular sieve, activated carbon and nano high polymer adsorption resin. The method for treating the isophorone dicarbamic acid n-butyl ester tail gas has the advantages that the n-butyl alcohol content in the tail gas is far lower than the industrial emission standard, no secondary pollution is caused, and the system safety is high.
Description
Technical Field
The invention relates to the technical field of IPDI (isophorone diisocyanate) synthesis, in particular to a method for removing n-butyl alcohol in tail gas in a process for synthesizing isophorone diamino acid n-butyl ester by a urea method.
Background
Isocyanate refers to a substance containing one or more NCO groups which reacts with a polyol to synthesize a polyurethane material. The current isocyanate mainly comprises MDI, TDI, HDI, IPDI, HMDI, XDI, NDI, PPDI, CHDI and other varieties. Of these, MDI and TDI are the two most prominent species at present, representing approximately 90% or more of the total amount of isocyanate, while HDI, IPDI and hydrogenated MDI have become more and more widespread in recent years due to their excellent weatherability and yellowing resistance.
IPDI (isophorone diisocyanate, CAS number 4098-71-9), a preferred starting material for the synthesis of photostable, weather-resistant polyamino acids, is a high-end product among the isocyanate starting materials. The polyurethane emulsion is mainly used in the fields of waterborne polyurethane dispersion, anticorrosive coatings, UV resins, adhesives, PU resins, printing ink and the like. And IPDI can also be used in the rocket propellant industry.
The IPDI production method mainly comprises a phosgene method and a thermal cracking method of carbamate, and the phosgene method is the main production method of diisocyanate at present. The phosgene method mainly comprises a liquid phase phosgene method and a gas phase phosgene method, but the liquid phase phosgene method has the disadvantages of long reaction time, large required solvent amount, low space-time efficiency of a reactor, more byproducts and relative lag behind; a series of engineering technical problems of safety, environmental protection and the like in the production process of the gas phase phosgene method are difficult to solve, the equipment corrosion is serious, the requirement on the equipment material is higher, the corresponding equipment investment is larger, and the obtained isocyanate product contains hydrolytic chlorine, so the service performance of the product is influenced. Therefore, developed countries have been devoted to developing economical and simple synthesis methods, and thus various non-phosgene methods for synthesizing isocyanates have appeared, such as carbonylation method, thermal decomposition of chlorinated formamide, rearrangement method of crutius, reaction method of amine and chlorinated formic ester, thermal decomposition method of carbamate, etc., but most of them are still in laboratory stage, and only the thermal decomposition method of carbamate realizes the installation production abroad. The urea process has the most studied route, is mature and is applied industrially. The process for preparing isocyanate by the urea method comprises two steps, namely reacting urea, diamine and alcohol to generate dicarbamate, and thermally cracking the dicarbamate to generate the isocyanate and the alcohol, wherein the total reaction yield can reach 90%.
The development and production of diisocyanate in China are relatively late, but with the rapid development of society and economy in China, the diisocyanate becomes a world-wide diisocyanate production and consumption country in China. On the other hand, in the field of high-performance special isocyanate, the development of China is very slow, and the consumption demand is increased at a speed of more than 15% per year. The aliphatic isocyanate is mainly applied to the fields of automobile finish, rocket propellant, anticorrosive paint, photocureable paint, adhesive and the like. Due to the historical reason of introducing technology, high-grade coatings for industries such as automobiles, high-speed trains, airplanes, steamships, luxury buses, wood furniture, buildings and the like in China are all occupied by foreign products, wherein one of the restriction factors is the key raw material aliphatic diisocyanate.
At present, HDI and IPDI in China have annual demand of about 9.5 ten thousand tons, are mainly occupied by a small number of international companies such as win-win companies, degussa companies and the like, the domestic product demand basically depends on import, and part of high-end military varieties are sold to the limit of China. The aliphatic diisocyanate is produced in China, particularly a non-phosgene method green synthesis technology is adopted, technical progress and industrial upgrading of related industries are promoted, the technology is necessary for guaranteeing industrial safety of important industries in China, and the method has great economic benefit and great social significance, but only 1 million tons per year of production devices are respectively built in Texaco and Basff by the non-phosgene method at present.
At present, IPDU-B (dimer of IPDI, molecular formula is:
) Still blank, IPDU-B production synthesis technology is always monopolized abroad, based on the great significance of IPDI on national economy and industry safety and the reality of backward production development in China,the applicant annually produced 2000 tons of non-phosgene process for the production of aliphatic (cyclo) group isocyanates (IPDI) project. In view of this, the invention provides a method for removing n-butanol from tail gas in a process for synthesizing isophorone diamino n-butyl formate by a urea method, so as to break through the technical monopoly of industrialized urea method IPDI synthesis in developed countries, not only eliminate the potential safety hazard of the phosgene method process from the root, but also have equal competitiveness with the phosgene method technology in the aspect of cost.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for removing n-butyl alcohol in tail gas in a process for synthesizing isophorone diamino acid n-butyl ester by a urea method, so as to at least achieve the effects that the content of the n-butyl alcohol in the tail gas is far lower than the industrial emission standard, no secondary pollution is caused and the system safety is high.
The purpose of the invention is realized by the following technical scheme:
the method for removing residual n-butanol contained in tail gas in the process of synthesizing isophorone carbamic acid n-butyl ester by adopting a urea method is characterized by comprising the following steps of:
the tail gas comes from: tail gas containing ammonia, which is obtained by a process for synthesizing isophorone diamino n-butyl ester by a urea method, is obtained by a process for removing ammonium carbamate;
the method for removing the residual n-butanol in the tail gas comprises the following steps: cooling the tail gas to 15-25 ℃, and adsorbing n-butyl alcohol in the tail gas by using an adsorbent;
the adsorbent comprises a molecular sieve, activated carbon and nano high polymer adsorption resin; preferably a nano-polymer adsorption resin.
Preferably, the nano polymer adsorption resin meets the following indexes: granularity (0.6-1.25 mm) > 95%, specific surface area > 1200 square meter/g, pore volume 0.88-0.98ml/g and pore diameter
Notably, the formation of the residual n-butanol is: in the process for synthesizing isophorone diamino n-butyl ester by the urea method, most of n-butyl alcohol is removed by an n-butyl alcohol deamination process, then the n-butyl alcohol is further removed by condensation through an ammonium carbamate removal process, but the remaining trace amount of n-butyl alcohol cannot be condensed;
further, the synthesis process of the isophorone diamino formic acid n-butyl ester comprises the following steps: carrying out an alkoxycarbonylation reaction of organic amine on IPDA (isophorone diamine, CAS No. 2855-13-2), n-butyl alcohol, urea and a catalyst (the IPDA is organic amine containing two amino groups), introducing carrier gas in the alkoxycarbonylation reaction process to separate a byproduct ammonia component, reacting to obtain n-butyl isophorone dicarbamate and synthesis tail gas containing the ammonia component, and carrying out an n-butyl alcohol deamination process on the synthesis tail gas;
the n-butanol deamination process comprises the following steps: separating the normal butanol and ammonia components in the synthetic tail gas by a rectification mode to obtain heavy component normal butanol and light component ammonia-containing tail gas.
Further, the process for removing ammonium carbamate from the ammonia-containing tail gas comprises the following steps: condensing ammonia-containing tail gas obtained by a process for synthesizing isophorone diamino n-butyl ester by a urea method to liquefy residual n-butyl alcohol in the ammonia-containing tail gas, and reacting carbon dioxide with an ammonia component to generate ammonium carbamate; separating materials from ammonium carbamate powder and n-butanol liquid obtained by condensation;
the material separation is as follows: after the condensation treatment, the material obtained by condensation is subjected to gas-liquid separation to obtain ammonia-containing tail gas containing ammonium carbamate powder and liquid-phase n-butanol, and then the ammonia-containing tail gas is subjected to gas-solid separation to remove the solid ammonium carbamate.
Further, the method for removing the residual n-butanol further comprises the following steps:
desorbing and regenerating the adsorbent by adopting high-temperature nitrogen to obtain a regenerated adsorbent and regenerated tail gas, and then condensing the regenerated tail gas to obtain liquid n-butyl alcohol and inert gas containing trace n-butyl alcohol;
further, the separated n-butanol is collected, and the inert gas containing the trace n-butanol is subjected to adsorption treatment again to separate the trace n-butanol.
Further, the temperature of the high-temperature inertia is 140-160 ℃.
Further, after the adsorbent adsorbs the butanol, the butanol tail gas is obtained, and the content of the n-butanol in the butanol tail gas is less than 12mg/m 3 。
Furthermore, at least two sets of adsorption units are arranged to alternately perform adsorption and desorption operations.
Further, the mole ratio of the IPDA, the n-butanol, the urea and the catalyst is 1:4-10:2-2.5:0.001-0.012; the reaction temperature of the alkoxy carbonylation reaction is 200-250 ℃, and the reaction pressure is 0.9-2.3MPa.
Preferably, the molar ratio of the IPDA, n-butanol, urea and the catalyst is 1:5-8:2-2.3:0.004-0.01; the reaction temperature of the alkoxycarbonylation reaction is 215-235 ℃; the reaction pressure is 1.2-1.5MPa
Further, the method comprises the following steps: at least one of zinc acetate, manganese acetate, zirconium acetate and cobalt acetate; preferably, the catalyst is zirconium acetate.
Further, the carrier gas is nitrogen.
The invention has the beneficial effects that:
1. the n-butanol content in the butanol-removed tail gas after adsorption is less than 12mg/m 3 Far below the environmental emission standard.
2. The separated desorption tail gas containing trace n-butanol and nitrogen is recycled to the front end of the desorption tower for reuse, so that secondary pollution is avoided.
3. The system has high safety, the service life of the adsorbent is as long as 3-5 years, and the adsorption rate of the n-butyl alcohol is high (more than 99%).
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to the following descriptions.
The equipment used was:
a reaction kettle: phi 1400×4253，5.4m 3 ；
A deamination tower: phi 500 is multiplied by 5000, and a flash tank phi 700 is multiplied by 1600;
falling film evaporator phi 1000 x 2500;
butanol adsorption tower: the diameter is 1800mm, the height is 2000mm, and the number is 3. The operating conditions are as follows: 30-150 deg.C (regeneration 150 deg.C), and micro-positive pressure.
Preparing raw materials:
urea: GB/T2440-2001 industrial superior product with actual purity of 99.6%
N-butanol: GB/T6027-1998 superior product with actual main content of 99.8%
IPDA: purity 99.5%
Catalyst (zirconium acetate): the purity is 99.0 percent
Process nitrogen gas: purity 99.0%
Example 1
Synthesizing isophorone diamino n-butyl formate by an industrial urea method, and removing n-butyl alcohol from tail gas, wherein the specific method comprises the following steps:
adding n-butyl alcohol, urea, IPDA and zirconium acetate into a reaction kettle, setting the reaction temperature of the reaction kettle to be 225 ℃ and the reaction pressure to be 1.45Mpa.G, and then carrying out reaction to obtain a product isophorone diamino n-butyl formate and synthetic tail gas containing carrier gas, n-butyl alcohol, ammonium carbamate and ammonia components. And (3) carrying out a n-butyl alcohol deamination process and a carbamate ammonia removal process on the synthesis tail gas to obtain the deamination ammonium formate tail gas containing residual n-butyl alcohol. Introducing the ammonium deamination formate tail gas into a precooler for cooling, keeping the outlet temperature at 20 ℃, pumping and pressurizing the cooled tail gas by a fan, and introducing the tail gas filled with nano adsorbent (the granularity (0.6-1.25 mm) > 95%, the specific surface area is 1400 square meters per gram, the pore volume is 0.90ml/g, and the pore diameter is 0.6-1.25 mm)
) The adsorption tower of (1). The absorbed tail gas of the butanol removal is introduced into a follow-up ammonia removal unit, the absorption is stopped when the absorption tower reaches the period time (three absorption towers are involved, one absorption tower is used, the other two absorption towers carry out desorption, the absorption and desorption processes are carried out alternately by switching between single doors, and the absorption tower is automatically switched to when reaching the penetration pointAnd in the desorption process), nitrogen with the temperature of 150 ℃ is adopted to desorb and regenerate the adsorbent, the desorbed ammonia gas containing the n-butyl alcohol is condensed and separated by using low-temperature chilled water, the separated liquid-phase n-butyl alcohol is collected to an n-butyl alcohol recovery tank, the gas phase containing trace n-butyl alcohol and nitrogen returns to the front end of the adsorption tower, and the gas phase is merged into the ammonium carbamate tail gas and passes through the adsorption tower to remove the trace n-butyl alcohol.
Comparative example 1
The method is characterized in that isophorone diamino n-butyl formate is synthesized by an industrialized urea method, and n-butyl alcohol is removed from tail gas, and the difference is that the adopted adsorbent is activated carbon.
Comparative example 2
The method is characterized in that isophorone diamino acid n-butyl ester is synthesized by an industrialized urea method, and n-butyl alcohol is removed from tail gas, and the difference is that the adopted adsorbent is a molecular sieve.
Experimental example 1
The tail gas of ammonium deamination formate in the reaction in the example 1 and the tail gas of butanol removal after absorption by the absorption tower are taken for detection, the content of n-butanol is detected by GC-FID, and statistics is shown in the following table.
| N-butanol (%) | |
| Tail gas of ammonium formate deamination | 1.20％ |
| Tail gas from the butanol removal | 0.001％ |
Experimental example 2
The butanol-removed tail gas obtained in example 1, comparative example 1 and comparative example 2 was taken, the n-butanol content in the butanol-removed tail gas was detected, and the adsorption rates of the three adsorbents were calculated, with the results shown in the following table.
| Adsorption rate | |
| Example 1 | 99.9％ |
| Comparative example 1 | 99.2％ |
| Comparative example 2 | 85.5％ |
Therefore, when the nano polymer adsorption resin is used as the adsorbent, the adsorption effect on the n-butanol is the best, and the adsorption rate is as high as 99.9%.
The foregoing is illustrative of the preferred embodiments of this invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the concept as disclosed herein, either as described above or as apparent to those skilled in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The method for removing residual n-butanol contained in tail gas in the process of synthesizing isophorone diamino acid n-butyl ester by adopting a urea method is characterized by comprising the following steps of:
the tail gas comes from: tail gas containing ammonia, which is obtained by a process for synthesizing isophorone diamino n-butyl ester by a urea method, is obtained by a process for removing ammonium carbamate;
the method for removing the residual n-butanol in the tail gas comprises the following steps: cooling the tail gas to 15-25 ℃, and adsorbing n-butyl alcohol in the tail gas by using an adsorbent;
the adsorbent comprises a molecular sieve, activated carbon and nano high polymer adsorption resin.
2. The removal method of claim 1, wherein the synthesis process of isophorone butyl dicarbamate comprises the following steps: carrying out an alkoxycarbonylation reaction of organic amine on IPDA, n-butyl alcohol, urea and a catalyst, introducing carrier gas in the alkoxycarbonylation reaction to separate a byproduct ammonia component, and reacting to obtain isophorone diamino acid n-butyl ester and synthetic tail gas, wherein the synthetic tail gas is subjected to an n-butyl alcohol deamination process;
the n-butanol deamination process comprises the following steps: separating the normal butanol and ammonia components in the synthetic tail gas by a rectification mode to obtain heavy-component normal butanol and light-component ammonia-containing tail gas.
3. The removal method according to claim 1, wherein the ammonia-containing tail gas is subjected to the removal process of ammonium carbamate, which comprises the following steps: condensing ammonia-containing tail gas obtained by a process for synthesizing isophorone diamino n-butyl ester by a urea method to liquefy residual n-butyl alcohol in the ammonia-containing tail gas, and reacting carbon dioxide with an ammonia component to generate ammonium carbamate; separating materials from ammonium carbamate powder and n-butanol liquid obtained by condensation;
the material separation is as follows: after the condensation treatment, the materials obtained by condensation are subjected to gas-liquid separation to obtain ammonia-containing tail gas containing ammonium carbamate powder and liquid-phase n-butyl alcohol, and then the ammonia-containing tail gas is subjected to gas-solid separation to remove solid ammonium carbamate.
4. According to claim 1The removing method is characterized in that: the n-butanol content in the butanol-removed tail gas after adsorption by the adsorbent is less than 12mg/m 3 。
5. The method of claims 1-4: further comprising the steps of:
and (2) carrying out desorption regeneration on the adsorbent by adopting high-temperature nitrogen to obtain a regenerated adsorbent and regenerated tail gas, and then condensing the regenerated tail gas to obtain liquid n-butanol and inert gas containing trace n-butanol.
6. The method of claim 5, wherein: the temperature of the high-temperature inertia is 140-160 ℃.
7. The removal method of claim 5, wherein: at least two sets of adsorption units are arranged to alternately perform adsorption and desorption operations.
8. The removal method according to claim 2, characterized in that: the mol ratio of the IPDA to the n-butanol to the urea to the catalyst is 1:4-10:2-2.5:0.001-0.012; the reaction temperature of the alkoxy carbonylation reaction is 200-250 ℃, and the reaction pressure is 0.9-2.3MPa.
9. The removal method of claim 2, wherein the catalyst comprises: at least one of zinc acetate, manganese acetate, zirconium acetate and cobalt acetate.
10. The removal method of claim 2, wherein: the carrier gas is nitrogen.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211208020.9A CN115779626A (en) | 2022-09-30 | 2022-09-30 | Method for removing residual n-butanol contained in tail gas in process of synthesizing isophorone diamino acid n-butyl ester by urea method |
| CN202311272565.0A CN117402084A (en) | 2022-09-30 | 2023-09-28 | Industrial IPDI synthesis process |
| CN202311272851.7A CN117342984A (en) | 2022-09-30 | 2023-09-28 | Method for removing residual n-butanol contained in tail gas in process of synthesizing isophorone dicarbamate by urea method |
| CN202311272700.1A CN117326982A (en) | 2022-09-30 | 2023-09-28 | Industrial process for synthesizing isophorone dicarbamic acid n-butyl ester by urea method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211208020.9A CN115779626A (en) | 2022-09-30 | 2022-09-30 | Method for removing residual n-butanol contained in tail gas in process of synthesizing isophorone diamino acid n-butyl ester by urea method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115779626A true CN115779626A (en) | 2023-03-14 |
Family
ID=85432461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211208020.9A Pending CN115779626A (en) | 2022-09-30 | 2022-09-30 | Method for removing residual n-butanol contained in tail gas in process of synthesizing isophorone diamino acid n-butyl ester by urea method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115779626A (en) |
-
2022
- 2022-09-30 CN CN202211208020.9A patent/CN115779626A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101062905B (en) | Process for the production of isocyanates | |
| WO2022041502A1 (en) | Preparation method for 1,5-pentane diisocyanate | |
| US8044166B2 (en) | Process for preparing pentamethylene 1,5-diisocyanate | |
| US8492580B2 (en) | Process for preparing isocyanates | |
| CN111263746B (en) | Method for producing ethyleneamines | |
| CN116589382A (en) | Industrial IPDI synthesis method | |
| JP7268016B2 (en) | Method for producing ethyleneamine | |
| CN115779626A (en) | Method for removing residual n-butanol contained in tail gas in process of synthesizing isophorone diamino acid n-butyl ester by urea method | |
| CN1554643A (en) | Method and apparatus for improving industrial producing urea | |
| CN103772240B (en) | Method for preparation of methylene diphenyl diisocyanate (MDI) | |
| CN117326984A (en) | Catalyst for synthesizing isophorone dicarbamic acid n-butyl ester technology by urea method | |
| CN115448855A (en) | Solvent used in isophorone diamino acid n-butyl ester industrial thermal cracking process | |
| CN115403484A (en) | Industrial process for synthesizing isophorone diamino n-butyl formate by urea method | |
| CN112574067B (en) | Method for preparing high-purity m-xylylene diisocyanate without phosgene | |
| CN117342984A (en) | Method for removing residual n-butanol contained in tail gas in process of synthesizing isophorone dicarbamate by urea method | |
| CA1236479A (en) | Process for the production of urethanes | |
| CN117326985A (en) | Industrialized synthesis process of isophorone dicarbamic acid n-butyl ester | |
| CN117326983A (en) | Method for removing ammonium carbamate in process of synthesizing isophorone dicarbamate n-butyl ester by urea method | |
| CN117326982A (en) | Industrial process for synthesizing isophorone dicarbamic acid n-butyl ester by urea method | |
| CN100415712C (en) | Process for producing methyl carbamate by low pressure solvation homogeneous phase reaction | |
| CN115433106A (en) | Industrialized synthesis process of isophorone diamino n-butyl formate | |
| CN115591578A (en) | Catalyst for synthesizing isophorone diamino n-butyl formate process by urea method | |
| CN109641175B (en) | Method for producing isocyanates | |
| CN117326980A (en) | Industrial method for producing IPDI by thermal cracking of isophorone dicarbamate | |
| CN100387570C (en) | Method for preparing diphenylamine by aniline liquid phase condensation and denitrification coupling |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20230314 |
|
| WD01 | Invention patent application deemed withdrawn after publication |