CN115569670A - Catalyst in industrial thermal cracking process of isophorone diamino formic acid n-butyl ester - Google Patents
Catalyst in industrial thermal cracking process of isophorone diamino formic acid n-butyl ester Download PDFInfo
- Publication number
- CN115569670A CN115569670A CN202211197042.XA CN202211197042A CN115569670A CN 115569670 A CN115569670 A CN 115569670A CN 202211197042 A CN202211197042 A CN 202211197042A CN 115569670 A CN115569670 A CN 115569670A
- Authority
- CN
- China
- Prior art keywords
- zinc
- catalyst
- isophorone
- thermal decomposition
- phase material
- 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
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 238000004227 thermal cracking Methods 0.000 title claims abstract description 38
- 230000008569 process Effects 0.000 title claims abstract description 22
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 33
- 229940046374 chromium picolinate Drugs 0.000 claims abstract description 16
- GJYSUGXFENSLOO-UHFFFAOYSA-N chromium;pyridine-2-carboxylic acid Chemical compound [Cr].OC(=O)C1=CC=CC=N1.OC(=O)C1=CC=CC=N1.OC(=O)C1=CC=CC=N1 GJYSUGXFENSLOO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000013132 MOF-5 Substances 0.000 claims abstract description 14
- 229940032991 zinc picolinate Drugs 0.000 claims abstract description 14
- NHVUUBRKFZWXRN-UHFFFAOYSA-L zinc;pyridine-2-carboxylate Chemical compound C=1C=CC=NC=1C(=O)O[Zn]OC(=O)C1=CC=CC=N1 NHVUUBRKFZWXRN-UHFFFAOYSA-L 0.000 claims abstract description 14
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims abstract description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002608 ionic liquid Substances 0.000 claims abstract description 6
- 239000004246 zinc acetate Substances 0.000 claims abstract description 6
- 239000011592 zinc chloride Substances 0.000 claims abstract description 6
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 6
- 239000011787 zinc oxide Substances 0.000 claims abstract description 6
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 claims abstract description 6
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 5
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 39
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 38
- 239000012071 phase Substances 0.000 claims description 29
- 239000007791 liquid phase Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- -1 n-butyl isophorone dicarbamate Chemical compound 0.000 claims description 6
- NMJJFJNHVMGPGM-UHFFFAOYSA-N n-butylmethanoate Natural products CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 claims description 5
- 239000010408 film Substances 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 2
- ROPPTGKKZZDFJN-UHFFFAOYSA-N trinonyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCCC)C(C(=O)OCCCCCCCCC)=C1 ROPPTGKKZZDFJN-UHFFFAOYSA-N 0.000 claims description 2
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 33
- 238000004519 manufacturing process Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 18
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 125000005442 diisocyanate group Chemical group 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000012948 isocyanate Substances 0.000 description 10
- 235000013877 carbamide Nutrition 0.000 description 9
- 150000002513 isocyanates Chemical class 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000013638 trimer Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001449342 Chlorocrambe hastata Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical group NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000007945 N-acyl ureas Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/04—Preparation of derivatives of isocyanic acid from or via carbamates or carbamoyl halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/18—Separation; Purification; Stabilisation; Use of additives
- C07C263/20—Separation; Purification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of industrial synthesis of IPDI (isophorone diisocyanate), in particular to a catalyst used in an industrial thermal cracking process of isophorone diamino acid n-butyl ester. The industrial catalyst is one or more of zinc picolinate, chromium picolinate, MOF-5, zinc oxide, bismuth trioxide, ionic liquid zinc, zinc chloride, zinc acetate, zinc acrylate and zinc isooctanoate. The zinc picolinate, the chromium picolinate and the MOF-5 are preferably selected, and when the zinc picolinate, the chromium picolinate and the MOF-5 are used for the industrial urea method isophorone diamino acid n-butyl ester thermal cracking catalyst, the catalyst has the effects of good selectivity, few side reactions and high product yield.
Description
Technical Field
The invention relates to the technical field of industrial synthesis of IPDI (isophorone diisocyanate), in particular to a catalyst used in an industrial thermal cracking process of isophorone diamino acid n-butyl ester.
Background
The chemical name of isophorone diisocyanate is 3-isocyanatomethylene-3, 5-trimethylcyclohexyl isocyanate, which is abbreviated as IPDI. Molecular formula C 12 H 18 N 2 O 2 Structural formula (II)The molecular weight is 222.29, the product is colorless or light yellow liquid, has camphoraceous odor, and is completely miscible with organic solvents such as ester, ketone, ether, aromatic hydrocarbon and aliphatic hydrocarbon.
Diisocyanates contain two-N = C = O groups, which are highly reactive due to electronic imbalance and unsaturation. The common chemical reactions are as follows:
reaction with water:
the reaction of diisocyanate with water to form unstable carbamic acid and rapidly decomposes to diisocyanate bulk diamine with evolution of carbon dioxide, which occurs at ambient temperature.
If the diisocyanate is in excess, the resulting diamine will continue to react with the diisocyanate to form urea and further react to form biuret.
OCNRCH 2 NCO+NH 2 RCH 2 NH 2 →OCNRCH 2 NHCONHRCH 2 NH 2
OCNRCH 2 NCO+OCNRCH 2 NHCONHRCH 2 NH 2
→OCNRCH 2 NHCONHRCH 2 NHCNHRCH 2 NCO
Reaction with hydroxyl groups:
in general, an OH-containing substance such as an alcohol or phenol reacts with a diisocyanate to form a urethane, and reacts with a dihydric or higher polyhydric alcohol to form a polyurethane.
OCNRNCO+2R'OH→R'OCONHRCH 2 NHCOOR'
This is also the principle of production of polyurethanes, which is the main use of diisocyanates.
Reaction with amine:
the reaction with primary and secondary amines produces substituted ureas (polyurea elastomers), while the tertiary amines do not contain active hydrogen and the diisocyanates do not react with the tertiary amines.
OCNRCH 2 NCO+NH 2 R'→CONRCH 2 NHCONHR'
OCNRCH 2 NCO+2NH 2 R'→R'NHOCNHRCH 2 NHCONHR'
OCNRCH 2 NCO+NHR'R"→CONRCH 2 NHCONR'R"
It is based on the above reaction that diamines are often used as cross-linking and chain extenders and triethylamine as neutralizing agent in the production of polyurethanes. On the other hand, in the cleavage units of HDI and IPDI, since the cleavage raw material dicarbamate contains two secondary amino groups (-NH), and the dicarbamate may contain amine and diamine and other amine substances in the by-product under high temperature conditions, IPDI as a product is reacted with the raw material and further polymerized. Thus, to the extent that the cleavage of the ADU to produce polyurethane is considered a reversible, bi-directional reaction, a pair of spearheads is utilized.
Reaction with Carbamate:
the reactivity is low and it takes more than 120 ℃ to react to produce allophanate product.
Reaction with acid anhydride:
the isocyanate reacts with the acid anhydride to form an imide ring having high heat resistance, and further reaction can form Polyimide (PI) having higher thermal stability.
Reaction with amide:
the isocyanate reacts with the amide to form an acylurea.
RNCO+H 2 NCOR'→RNHCONHCOR'
Self-polymerization reaction:
IPDI undergoes self-polymerization under the action of heat and a catalyst (such as dibutyltin dilaurate), and dimers, trimers and even polymers are formed at higher temperatures.
Two IPDIs self-polymerize into IPDI dimer:
the dimer is an unstable compound and decomposes to IPDI by heating, or continues to polymerize to a trimer.
Unlike dimers, the reaction of trimers is irreversible and the thermal decomposition products of trimers are not IPDI. The trimer has the advantages of stable structure, difficult decomposition at high temperature, good thermal stability, good wear resistance, good corrosion resistance and the like, can quickly release a solvent, has higher reaction activity because the trimer still contains a group with-N = C = O, and is often used as a polyurethane curing agent to be widely applied to industries such as furniture, automobiles, aviation and the like.
The production method of isophorone diisocyanate mainly comprises a phosgene method and a thermal cracking method of carbamate. The phosgene method is still the main production method of diisocyanate at present, only 1 million tons per year of production devices are respectively built in the non-phosgene method of only Degussa and Basff, and domestic production is still blank.
The gas phase phosgenation process is a process for preparing isocyanate by diluting gaseous amines with inert gas or steam of inert solvent, feeding them into a mixing reactor together with phosgene, and reacting at 200-600 ℃. The gas phase method is a latest phosgenation method, and compared with the traditional liquid phase phosgenation method, the gas phase method has the advantages of less phosgene usage, extremely fast reaction rate, high yield (more than 98 percent) and low risk. At present, bayer uses this method to produce HDI and IPDI, and the yield accounts for more than 70% of HDI production. The process is also adopted by the only IPDI production enterprises in China.
The amine phosgene method mainly has the following problems: (1) phosgene is a highly toxic gas, and a series of engineering technical problems of safety, environmental protection and the like in the production process are difficult to solve; (2) a large amount of byproduct hydrogen chloride exists in the production of the phosgene method, and if the absorption treatment is incomplete, the hydrogen chloride also leaks to cause environmental pollution; (3) the byproduct hydrogen chloride has serious corrosion to equipment in the production process, has higher requirements on equipment materials and has larger corresponding equipment investment; (4) isocyanate products produced by a phosgene method contain hydrolytic chlorine, and the service performance of the products is influenced.
Since the phosgene method has the above-mentioned disadvantages, developed countries have been devoted to developing an economical and simple synthesis method, and thus various non-phosgene methods for synthesizing isocyanates have appeared, such as carbonylation, thermal decomposition of chlorinated formamide, rearrangement, reaction of amine and chlorinated formic ester, thermal decomposition of carbamic acid ester, etc., but most of them are still in the laboratory stage, and only the thermal decomposition of carbamic acid ester realizes the production in facilities abroad.
The starting materials for the preparation of carbamates include, inter alia, the urea process and the dialkyl carbonate process.
The process for preparing carbamate by dimethyl carbonate and preparing ADI by thermal cracking attracts attention, and the method has the characteristics of easy reaction, simple control and high yield, and the generated methanol can be recycled to further prepare the dimethyl carbonate. However, the manufacturing cost of dimethyl carbonate is high, which limits the industrial application of the method.
The urea route has been studied most, the process is mature and has been used industrially (abroad). 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 thermal cracking reaction may be carried out in the liquid phase or in the gas phase. The gas phase thermal cracking is a high-temperature process, generally the temperature is higher than 300 ℃, and the reaction can be carried out with or without a catalyst; the liquid phase thermal cracking process is generally carried out at temperatures below 300 deg.C, usually with the addition of a catalyst and a high boiling point solvent. Thermal decomposition is often accompanied by the formation of many side reactions, such as tars, resinous polymeric byproducts, which not only reduce yield, but also plug reactors and other equipment.
The development and production of diisocyanate in China are relatively late, but along with the rapid development of society and economy in China, the diisocyanate becomes a world-wide production and consumption country, wherein MDI and TDI account for more than 85% of the total amount of diisocyanate. 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 by more than 15% per year. The aliphatic isocyanate is mainly applied to the fields of automobile finish, rocket propellant, anticorrosive coating, photocureable coating, 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 need about 9.5 ten thousand tons in year, and are mainly occupied by a few international companies such as winning and creating, degussa and the like. HDI is built with 3 million tons/year, 1.5 million tons/year smoke station, and most products of Bayer are exported and the price is high; IPDI is only used for building 1.5 million tons per year of devices in the world by adopting a phosgene method, the operation is abnormal all the time, and only a small amount of products enter the market. The domestic product requirements basically depend on import, and due to well-known reasons, part of high-end military varieties are sold to the limit of China.
Based on the great significance of IPDI to national economy and industry safety and the fact that the domestic production development lags behind, the applicant produces 2000 tons of non-phosgene method production aliphatic (cyclo) group isocyanate (IPDI) project annually. The invention provides a catalyst for thermal cracking of industrial isophorone diamino n-butyl formate, which breaks the technical monopoly of IPDI (isophorone diisocyanate) synthesized by an industrial urea method in developed countries.
Disclosure of Invention
The invention aims to provide an industrial catalyst used in a thermal cracking process of isophorone dicarbamic acid n-butyl ester.
The purpose of the invention is realized by the following technical scheme:
the catalyst in the industrial thermal cracking process of isophorone dicarbamic acid n-butyl ester is one or more of zinc picolinate, chromium picolinate, MOF-5, zinc oxide, bismuth trioxide, ionic liquid zinc, zinc chloride, zinc acetate, zinc acrylate and zinc isooctanoate.
Further, the catalyst is one or more of zinc picolinate, chromium picolinate and MOF-5. Zinc picolinate, chromium picolinate and MOF-5 are required to meet food grade or industrial grade standards.
The invention also provides application of the industrial catalyst in an industrial thermal cracking process of isophorone diamino formic acid n-butyl ester, wherein the thermal cracking process is carried out by adopting a liquid phase method.
Further, the thermal cracking process comprises the following steps:
carrying out a first thermal decomposition reaction on isophorone diamino n-butyl formate, a solvent and a catalyst to obtain a gas-phase material I, carrying out rectification operation on the gas-phase material I to obtain a gas-phase material II and a liquid-phase material II, carrying out a second thermal decomposition reaction on the liquid-phase material II to obtain a gas-phase material III, and returning the gas-phase material III to the rectification operation, wherein the gas-phase material II is an IPDI product.
Further, the pressure of the first thermal decomposition reaction is controlled to be-0.08 to-0.098 MPa, and the temperature is controlled to be 200 to 280 ℃;
and/or the pressure controlled by the second thermal decomposition reaction is-0.08 to-0.098 MPa, and the temperature is 200 to 280 ℃.
Furthermore, the pressure of the first thermal decomposition reaction is controlled to be-0.092 to-0.098 MPa, and the temperature is controlled to be 220 to 260 ℃;
and/or the pressure controlled by the second thermal decomposition reaction is-0.092 to-0.098 MPa, and the temperature is 220 to 260 ℃.
Furthermore, the temperature of the second thermal decomposition reaction is 1-10 ℃ higher than that of the first thermal decomposition reaction, preferably 4-8 DEG C
Further, the mass ratio of the isophorone diamino n-butyl formate, the solvent and the catalyst is as follows: 1:0-9:0.0025-0.015. Preferably, the mass ratio of the isophorone diamino n-butyl formate to the solvent to the catalyst is as follows: 1:0.67-9:0.003-0.010.
Further, the n-butyl isophorone dicarbamate is an n-butyl isophorone dicarbamate product synthesized by a urea method;
and/or the solvent is one of naphthenic oil, trioctyl trimellitate and trinonyl trimellitate.
Further, the step of rectifying operation comprises:
s1, feeding the gas-phase material I and the gas-phase material III into a first rectifying tower for rectifying, and extracting an IPDI (isophorone diisocyanate) rich solution from the middle part of the first rectifying tower; the operating pressure of the first rectifying tower is 10-30mbar, the temperature of a tower kettle is 190-210 ℃, the operating temperature of a tower top is 20-30 ℃, and the temperature of a tower middle part is 150-170 ℃;
s2, feeding the IPDI rich solution into a second rectifying tower for rectification, and extracting an IPDI product from the middle part of the second rectifying tower; the operating pressure of the second rectifying tower is 10-30mbar, the temperature of the tower kettle is 190-200 ℃, the operating temperature of the tower top is 30-50 ℃, and the temperature of the tower middle part is 155-160 ℃.
Further, n-butanol is extracted from the top of the first rectifying tower, and n-butanol and IPDI are extracted from the top of the second rectifying tower; and performing a second thermal decomposition reaction on the material mixed liquid phase material II at the tower bottoms of the first rectifying tower and the second rectifying tower.
Further, the reactor of the first thermal decomposition reaction and/or the second thermal decomposition reaction is a thin film evaporator. Preferably, the thin film evaporator is a wiped film evaporator.
Furthermore, heavy component materials are obtained through the first thermal decomposition reaction and the second thermal decomposition reaction, and the heavy component materials need to be discharged through the first thermal decomposition reaction and the second thermal decomposition reaction.
Further, the discharged heavy component material is heated and evaporated to obtain a gas-phase product and a residue, and the gas-phase product can be used as a solvent for the first thermal decomposition reaction or the second thermal decomposition reaction after being condensed.
The invention has the beneficial effects that:
the zinc picolinate, the chromium picolinate and the MOF-5 are used for the industrial urea method isophorone dicarbamic acid n-butyl ester thermal cracking catalyst, and have the effects of good selectivity, few side reactions and high product yield.
Drawings
FIG. 1 is a flow chart of the thermal cracking process of isophorone carbamic acid n-butyl ester of the present invention.
Detailed Description
The technical solutions of the present invention are described in further detail below, but the scope of the present invention is not limited to the following.
1. Reactor, reaction process, raw materials and detection method for laboratory and industrial IPDU-B thermal cracking
(1) Laboratory thermal cracking reactor
A cracker: evaporation area 0.1m 2 ;
Circulating pump: the gear pump is 2.8L/h;
a rectification column: phi 50 is multiplied by 800;
(2) Laboratory thermal cracking reaction process
The raw material enters a film evaporator (a cracker) to be heated and cracked (namely, the first thermal cracking reaction), and the IPDU-B and naphthenic oil which are not decomposed at the lower part and a small amount of IPDI are sent back to an inlet at the upper part of the cracker through a circulating pump. Pyrolysis gas (gas phase material I) from the upper part of the cracker enters a rectifying column under the action of vacuum, heavy components (liquid phase material II) flow back into the cracker (namely, second thermal cracking reaction) from the lower part of the rectifying column, pyrolysis gas (gas phase material III) from the upper part of the cracker enters the rectifying column under the action of vacuum, light components (gas phase material II) enter a heat exchanger from the upper part of the rectifying column, and the light components (gas phase material II) automatically flow into a crude product tank after being condensed. The thermal cracking temperature is 240 ℃, the operation pressure is-0.094Mpa, the addition amount of IPDU-B is 500g, and the addition amount of naphthenic oil KN4010 is 500g. ( Note: the first thermal cracking reaction and the second thermal cracking reaction are separately carried out in the same equipment, and the cracker is operated discontinuously )
(3) Industrial thermal cracking reactor
IPDU-B feedstock pump: q =2m 3 H, H =14m;1# cracker: a =30m 2 (ii) a 1# cracking circulating pump: q =5m 3 H, H =14m;1# Polymer Drain Pump: q =2m 3 H, H =14m;2# cracker: a =25m 2 (ii) a 2# cracking circulating pump: q =5m 3 H, H =14m;2# high polymer positive displacement pump: q =2m 3 /h,H=14m。
(4) Industrial thermal cracking reaction process
Feeding the thermal decomposition raw material IPDU-B, a solvent and a catalyst into a No. 1 rotating scraper thermal decomposition reactor (first thermal decomposition reaction), forcibly forming a liquid film on the inner wall of the reactor through a rotating scraper, and heating through the inner wall of the reactor to carry out the thermal decomposition reaction. Under the vacuum condition, the thermal decomposition product is quickly evaporated to realize the quick separation with the reaction raw material, thereby greatly reducing the generation of side reaction. And (3) removing the entrained liquid-phase material from the gas-phase material (gas-phase material I, reaction product) at the outlet of the reactor through a gas-liquid separator, and feeding the liquid-phase material into a rectification unit. And (3) feeding the material (mainly single side) in the distillation tower kettle into a 2# rotary scraper thermal decomposition reactor for thermal decomposition reaction (second thermal decomposition reaction), removing the entrained liquid phase material (gas phase material III, reaction product) from the outlet of the reactor through a gas-liquid separator, feeding the liquid phase material into a distillation unit, and obtaining a gas phase material II by the distillation unit. The bottom of the two reactors is provided with a circulating tank and a circulating pump, and the solvent and the catalyst are circulated.
(5) Raw materials
Isophorone diamino formic acid n-butyl ester (IPDU-B) component: the internal control index is more than or equal to 99.0 percent (IPDU-B99.38 percent, catalyst for synthesizing IPDU-B0.46 percent, other 0.16 percent);
thermal cracking reaction catalyst: zinc picolinate, chromium picolinate, MOF-5, zinc oxide, bismuth trioxide, ionic liquid zinc, zinc chloride, zinc acetate, zinc acrylate and zinc isooctanoate;
solvent: naphthenic oil KN4010.
(6) Detection method
See table 1:
TABLE 1
2. Screening experiment of catalyst
(1) Experiment for screening of catalyst species
Selecting a laboratory thermal cracking reactor and a reaction flow, wherein the dosage of the catalyst is 3.5g, and the catalyst is zinc picolinate, chromium picolinate, MOF-5, zinc oxide, bismuth trioxide, ionic liquid zinc, zinc chloride, zinc acetate, zinc acrylate and zinc isooctanoate, respectively, carrying out experiments according to the experimental conditions, and determining the properties of the thermal cracking product, wherein the experimental results are shown in the following table 2:
TABLE 2
Experiment batch number | Catalyst and process for preparing same | Reaction completion time (min) | IPDI yield (%) | Colloid ratio (%) |
Group 1-1 | Chromium picolinate | 45 | 91.59 | 2.65 |
Groups 1 to 2 | MOF-5 | 33 | 92.02 | 3.58 |
Groups 1 to 3 | Zinc picolinate | 37 | 91.32 | 3.49 |
Groups 1 to 4 | Zinc oxide | 44 | 79.04 | 9.24 |
Groups 1 to 5 | Bismuth oxide | 49 | 57.04 | 10.06 |
Groups 1 to 6 | Ionic liquid zinc | 75 | 49.07 | 14.68 |
Groups 1 to 7 | Zinc chloride | 43 | 53.06 | 13.88 |
Groups 1 to 8 | Zinc acetate | 55 | 56.72 | 13.68 |
Groups 1 to 9 | Acrylic acid zinc salt | 52 | 59.79 | 12.45 |
Groups 1 to 10 | Zinc iso-octoate | 54 | 60.95 | 12.68 |
Note: the main components of the colloid in the invention are catalyst and high molecular polymer (by-product); the ratio of the gum to the amount of IPDU-B fed is referred to as the ratio of the gum production to the amount of IPDU-B fed.
As is clear from Table 2, the catalysts shown in groups 1 to 10 all have a certain catalytic effect, but when chromium picolinate, MOF-5 and zinc picolinate are selected as the catalysts, the yield of IPDI is high and the content of colloidal substances is low (side reactions are small), and therefore, chromium picolinate, MOF-5 or zinc picolinate is preferably used as the catalyst in the present invention.
(2) Catalyst dosage screening experiment
The operating conditions are as follows: selecting a laboratory thermal cracking reactor and a reaction flow, and controlling the cracking temperature of the cracker to 240 ℃; the operation pressure is-0.094 MPa; 500g of IPDU-B and 500g of naphthenic oil are added, the catalyst is chromium picolinate, and a catalyst dosage screening experiment is carried out, wherein the dosage screening result of the catalyst is shown in the following table 3:
TABLE 3
Note: the amount (% by mass) of the catalyst is based on the amount of IPDU-B.
As can be seen from the data in Table 3, when the catalyst is used in an excessive or insufficient amount, the IPDI yield decreases and the colloidal material increases, and the most suitable amount of the catalyst is 0.3% to 1%.
(3) Verification of effect of industrial IPDU-B thermal cracking reaction
The operating conditions are as follows: selecting an industrial thermal cracking reactor and a reaction flow, and controlling IPDU-B through circulation quantity and supplement quantity: naphthenic oil KN4010: the mass ratio of chromium picolinate is 1:1:0.007; 4 batches were carried out on an industrial plant. The statistical results are shown in table 4 below.
TABLE 4
As can be seen from Table 4, the yield of IPDI in industrial production is more than 91%, which proves that the effect of the catalyst of the present invention is verified in the feasibility of industrialization.
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 catalyst in the industrial thermal cracking process of isophorone dicarbamic acid n-butyl ester is characterized in that the industrial catalyst is one or more of zinc picolinate, chromium picolinate, MOF-5, zinc oxide, bismuth trioxide, ionic liquid zinc, zinc chloride, zinc acetate, zinc acrylate and zinc isooctanoate.
2. The catalyst of claim 1, wherein the catalyst is one or more of zinc picolinate, chromium picolinate, and MOF-5.
3. Use of the industrial catalyst of any one of claims 1 to 2 in an industrial thermal cracking process of isophorone dicarbamic acid n-butyl ester, wherein the thermal cracking process is carried out using a liquid phase method for the preparation of IPDI.
4. Use according to claim 3, wherein the thermal cracking process comprises the steps of:
carrying out a first thermal decomposition reaction on isophorone diamino n-butyl formate, a solvent and a catalyst to obtain a gas-phase material I, carrying out rectification operation on the gas-phase material I to obtain a gas-phase material II and a liquid-phase material II, carrying out a second thermal decomposition reaction on the liquid-phase material II to obtain a gas-phase material III, and returning the gas-phase material III to the rectification operation, wherein the gas-phase material II is an IPDI product.
5. The use according to claim 4, wherein the first thermal decomposition reaction is controlled at a pressure of-0.08 to-0.098 MPa and a temperature of 200 to 280 ℃;
the pressure of the second thermal decomposition reaction is controlled to be-0.08 to-0.098 MPa, and the temperature is controlled to be 200 to 280 ℃.
6. Use according to claim 5, wherein the temperature of the second thermal decomposition reaction is 1-10 ℃ higher than the temperature of the first thermal decomposition reaction.
7. The use according to claim 4, wherein the mass ratio of isophorone dicarbamic acid n-butyl ester, solvent and catalyst is: 1:0-9:0.0025-0.015.
8. The use of claim 4, wherein the n-butyl isophorone dicarbamate is a product of n-butyl isophorone dicarbamate synthesized by a urea process;
and/or the solvent is one of naphthenic oil, trioctyl trimellitate and trinonyl trimellitate.
9. Use according to claim 4, wherein the reactor of the first thermal decomposition reaction and/or the second thermal decomposition reaction is a thin film evaporator.
10. Use according to claim 9, wherein the thin film evaporator is a wiped film evaporator.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211197042.XA CN115569670A (en) | 2022-09-29 | 2022-09-29 | Catalyst in industrial thermal cracking process of isophorone diamino formic acid n-butyl ester |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211197042.XA CN115569670A (en) | 2022-09-29 | 2022-09-29 | Catalyst in industrial thermal cracking process of isophorone diamino formic acid n-butyl ester |
Publications (1)
Publication Number | Publication Date |
---|---|
CN115569670A true CN115569670A (en) | 2023-01-06 |
Family
ID=84584076
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211197042.XA Pending CN115569670A (en) | 2022-09-29 | 2022-09-29 | Catalyst in industrial thermal cracking process of isophorone diamino formic acid n-butyl ester |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115569670A (en) |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101234998A (en) * | 2006-12-23 | 2008-08-06 | 赢创德固赛有限责任公司 | Process for the continuous preparation of (cyclo) aliphatic diisocyanates |
CN101530785A (en) * | 2009-04-21 | 2009-09-16 | 山东润兴化工科技有限公司 | Composite catalyst for preparing isocyanate by pyrolyzing aminoalkyl esters |
CN101962348A (en) * | 2009-07-23 | 2011-02-02 | 中国科学院兰州化学物理研究所 | Method for preparing isocyanate by liquid thermal cracking |
US20110313192A1 (en) * | 2010-06-22 | 2011-12-22 | Basf Se | Heterogeneously catalyzed carbamate dissociation for synthesis of isocyanates over solid lewis acids |
KR20140042303A (en) * | 2012-09-28 | 2014-04-07 | 코오롱인더스트리 주식회사 | Method for preparing aliphatic diisocyanates |
CN103965079A (en) * | 2014-05-23 | 2014-08-06 | 上海沣勃新材料科技有限公司 | Method for continuously preparing aliphatic or cyclic diisocyanate |
CN104117358A (en) * | 2014-05-23 | 2014-10-29 | 上海沣勃新材料科技有限公司 | Compound catalyst and method for synthesizing aliphatic or cyclic diisocyanate in presence of catalyst |
CN105728033A (en) * | 2016-04-19 | 2016-07-06 | 安徽华荣高科新材料股份有限公司 | Application of catalyst for thermal decomposition of aliphatic or cycloaliphatic dicarbamate |
CN105801450A (en) * | 2016-04-19 | 2016-07-27 | 安徽华荣高科新材料股份有限公司 | System integrating fatty group or ring group diisocyanate synthesis and separation and purification and synthesis method |
CN109734626A (en) * | 2019-01-03 | 2019-05-10 | 中国科学院兰州化学物理研究所 | A kind of thermal cracking isocyanates forms the depolymerization method of polymer in the process |
CN115572245A (en) * | 2022-09-29 | 2023-01-06 | 四川元理材料科技有限公司 | Industrial method for producing IPDI (isophorone diisocyanate) by thermal cracking of n-butyl isophorone dicarbamate |
-
2022
- 2022-09-29 CN CN202211197042.XA patent/CN115569670A/en active Pending
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101234998A (en) * | 2006-12-23 | 2008-08-06 | 赢创德固赛有限责任公司 | Process for the continuous preparation of (cyclo) aliphatic diisocyanates |
CN101530785A (en) * | 2009-04-21 | 2009-09-16 | 山东润兴化工科技有限公司 | Composite catalyst for preparing isocyanate by pyrolyzing aminoalkyl esters |
CN101962348A (en) * | 2009-07-23 | 2011-02-02 | 中国科学院兰州化学物理研究所 | Method for preparing isocyanate by liquid thermal cracking |
US20110313192A1 (en) * | 2010-06-22 | 2011-12-22 | Basf Se | Heterogeneously catalyzed carbamate dissociation for synthesis of isocyanates over solid lewis acids |
KR20140042303A (en) * | 2012-09-28 | 2014-04-07 | 코오롱인더스트리 주식회사 | Method for preparing aliphatic diisocyanates |
CN103965079A (en) * | 2014-05-23 | 2014-08-06 | 上海沣勃新材料科技有限公司 | Method for continuously preparing aliphatic or cyclic diisocyanate |
CN104117358A (en) * | 2014-05-23 | 2014-10-29 | 上海沣勃新材料科技有限公司 | Compound catalyst and method for synthesizing aliphatic or cyclic diisocyanate in presence of catalyst |
CN105728033A (en) * | 2016-04-19 | 2016-07-06 | 安徽华荣高科新材料股份有限公司 | Application of catalyst for thermal decomposition of aliphatic or cycloaliphatic dicarbamate |
CN105801450A (en) * | 2016-04-19 | 2016-07-27 | 安徽华荣高科新材料股份有限公司 | System integrating fatty group or ring group diisocyanate synthesis and separation and purification and synthesis method |
CN109734626A (en) * | 2019-01-03 | 2019-05-10 | 中国科学院兰州化学物理研究所 | A kind of thermal cracking isocyanates forms the depolymerization method of polymer in the process |
CN115572245A (en) * | 2022-09-29 | 2023-01-06 | 四川元理材料科技有限公司 | Industrial method for producing IPDI (isophorone diisocyanate) by thermal cracking of n-butyl isophorone dicarbamate |
Non-Patent Citations (2)
Title |
---|
刘喆等: "非光气法制备 HDI工艺研究进展", 《天然气化工 C1化学与化工》, pages 95 * |
张毅等: "硝基修饰 MOF-5材料的制备及催化氨基甲酸酯热分解", 《高等学校化学学报》, pages 2 - 6 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN115572245A (en) | Industrial method for producing IPDI (isophorone diisocyanate) by thermal cracking of n-butyl isophorone dicarbamate | |
JP5377660B2 (en) | Isocyanate production method | |
CN113993928A (en) | Process for recovering raw materials from polyurethane products | |
JP2009545553A (en) | Method for producing pentamethylene-1,5-diisocyanate | |
JPH0641045A (en) | Continuous multistage production of (cyclo)aliphatic diisocyanate | |
CN101928235A (en) | Method for continuously preparing 1,6-hexamethylene diisocyanate | |
CN110511163B (en) | Method for preparing polyisocyanate by photochemical reaction and method for preparing aqueous polyurethane resin | |
EP1634868A2 (en) | Multistep process for the continuous preparation of cycloaliphatic diisocyanates | |
EP2493850A1 (en) | Method for the combined production of diisocyanates and/or polyisocyanates and glycols | |
WO2011078000A1 (en) | Method for treatment of isocyanate residue, and method for treatment of carbonate | |
CN115433105A (en) | Industrial method for preparing IPDI (IPDI) by pyrolysis method | |
EP2480525B1 (en) | Method for producing isocyanates | |
CN115448855A (en) | Solvent used in isophorone diamino acid n-butyl ester industrial thermal cracking process | |
EP1926707B1 (en) | Process for the preparation of isocyanates | |
DE102007039127A1 (en) | Process for the preparation of isocyanates | |
US4405527A (en) | Process for the preparation of polyisocyanates | |
US3264336A (en) | Purification of isocyanates by reduction of the hydrolyzable chlorine and acid content | |
CN101200436A (en) | Method for continuously preparing 1,6-hexamethyl diisocyanate | |
CN115569670A (en) | Catalyst in industrial thermal cracking process of isophorone diamino formic acid n-butyl ester | |
US8609887B2 (en) | Process for preparing polyisocyanates comprising biuret groups | |
CN115433086A (en) | Industrial recovery method of solvent in isophorone diamino formic acid n-butyl ester pyrolysis reaction | |
CN115611776A (en) | Industrial method for purifying IPDI (isophorone diisocyanate) crude product | |
CN1188445C (en) | Method for preparing polyiso cyanate with biuret structure | |
US4278805A (en) | Process for the preparation of an aryl mono-, di-, and/or polyurethane | |
CN117323936A (en) | Industrial recovery method of solvent in pyrolysis reaction of isophorone dicarbamic acid n-butyl ester |
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 |