CN105218422B - Preparation method of isocyanate - Google Patents
Preparation method of isocyanate Download PDFInfo
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- CN105218422B CN105218422B CN201510672466.0A CN201510672466A CN105218422B CN 105218422 B CN105218422 B CN 105218422B CN 201510672466 A CN201510672466 A CN 201510672466A CN 105218422 B CN105218422 B CN 105218422B
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 39
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 181
- 239000002002 slurry Substances 0.000 claims abstract description 158
- 239000007788 liquid Substances 0.000 claims abstract description 124
- 150000003839 salts Chemical class 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 46
- -1 amine hydrochlorides Chemical class 0.000 claims abstract description 27
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 86
- 150000001412 amines Chemical class 0.000 claims description 75
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 61
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 61
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 54
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- 238000007599 discharging Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 230000005070 ripening Effects 0.000 claims description 18
- 239000000376 reactant Substances 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 5
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 14
- 238000006552 photochemical reaction Methods 0.000 abstract description 11
- 125000003277 amino group Chemical group 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 69
- 239000002245 particle Substances 0.000 description 48
- 239000000047 product Substances 0.000 description 34
- 238000002347 injection Methods 0.000 description 17
- 239000007924 injection Substances 0.000 description 17
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 16
- 230000008569 process Effects 0.000 description 15
- 239000006227 byproduct Substances 0.000 description 14
- 239000007791 liquid phase Substances 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000009826 distribution Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000011324 bead Substances 0.000 description 7
- 238000010008 shearing Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 235000013877 carbamide Nutrition 0.000 description 5
- 238000005253 cladding Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CKDWPUIZGOQOOM-UHFFFAOYSA-N Carbamyl chloride Chemical compound NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000007792 gaseous phase Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 150000003672 ureas Chemical class 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- 125000000266 alpha-aminoacyl group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 description 1
- 101710130081 Aspergillopepsin-1 Proteins 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000013094 purity test Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001839 systemic circulation Effects 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- WOZVHXUHUFLZGK-UHFFFAOYSA-N terephthalic acid dimethyl ester Natural products COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing isocyanate based on a salifying phosgenation method. A salt forming reaction in the method comprises the following two steps: firstly, performing preliminary salt forming reaction by adopting a conventional reactor; secondly, adding a moderately polar organic solvent with a certain proportion into a reactor provided with an hourglass type liquid slurry disperser to carry out salt forming curing reaction, wherein star-shaped discharge openings are arrayed in a cylinder body of the hourglass type disperser. According to the preparation method, the fact that amino groups in raw materials are converted into amine hydrochlorides with high conversion rate can be ensured through the salt forming curing reaction, and the isocyanate product can be obtained with high yield through a follow-up photochemical reaction.
Description
Technical field
The present invention relates to a kind of preparation method of isocyanates, prepares Carbimide. more particularly by into salt light phosgenation
The method of ester, belongs to light phosgenation and prepares isocyanates field.
Background technology
Isocyanates are the speciality chemicals that a class has-N=C=O functional groups, and the height of-N=C=O functional groups reacts lives
Property makes which be widely used as the fine chemical product such as pesticide, medicine synthetic intermediate and polyurethane material synthesis material.With Carbimide.
Ester is more various in style with which for the polyurethane material of base stock, flexible and changeable, and building, car are applied to the characteristics of different properties
, household electrical appliance, space flight and aviation, electromechanics, ship, chemical industry, metallurgical mining, light industry, weaving, national economy and the state such as health care
Anti- construction every field.
Fatty (ring) race isocyanates (ADI) is-N=C=O functional groups in molecular structure and fat (ring) race group phase
Special isocyanate products even, ADI and polyether polyol or PEPA reacted polymerization and obtained polyurethane products,
With the good application performance such as non yellowing, it is widely used as industry and automobile polyurethane coating, has obtained extensive pass in recent years
Note.
It is XDI (XDI) to compare a special product in ADI, and molecular formula is C10H8N2O2, point
Son amount is 188.19, and its major industrialized product has m-xylylene diisocyanate (m-XDI), terephthalylidene two different
Cyanate (p-XDI), structural formula is respectively：
XDI vapour pressures are relatively low, and reactivity is higher, due in its molecular structure NCO functional groups without directly with phenyl ring phase
Even, and by methylene (- CH2-) be separated by, it is therefore prevented that resonate between phenyl ring and NCO group so that XDI and its polyurethane product pair
Light is stable, non yellowing.Can be used for high-grade polyurethane coating, elastomer, leather, adhesive, lenses etc..
At present, many about the preparation technology report of ADI, disclosed mainstream technology is organic amine and phosgene reaction system
Standby isocyanates.Additionally, also disclosing some other method.The clear 52-46042 of Japanese Laid-Open Patent is disclosed in copper class catalyst and deposits
Under, the method for the aromatic with chloromethyl and alkaline cyanic acid reactant salt；United States Patent (USP) US4207251 is disclosed in catalytic gold
In the presence of category, the gas phase law technology that the Methanamide that N- replaces is aoxidized by oxygen-containing gas；Chinese patent CN103351313A,
CN101805271A, CN102827035A, CN102659632A disclose the synthesis technique that triphosgene prepares ADI, use
Triphosgene carries out reaction under catalytic condition with fatty (ring) race's diamidogen or its hydrochlorate and prepares ADI.
Above non-phosgene chemical industry skill is all because yield is low, process route is complicated and economy problems fail industrialized production, existing
There is phosgenation technology to be broadly divided into gas phase phosgenation technology and liquid phase phosgenation technology.
Gas phase phosgenation technology is needed amine high-temperature heating to gas phase state, needs amine low boiling point, gasifiable, amine in gas phase
Can be with stable existence under state, operating in addition is carried out at high temperature under high pressure, and technological difficulty is larger.
Liquid phase phosgenation technology is divided into direct light phosgenation and into salt light phosgenation, and direct light phosgenation is by primary amine and light
Gas direct reaction is obtained corresponding isocyanates, and direct light phosgenation has a drawback, when the reactivity of amine is high, generation
Isocyanates meeting and free amino reaction generate ureas by-product.Into salt light phosgenation, it is necessary first to by amine and sour gas
As hydrogen chloride, carbon dioxide reaction are obtained hydrochloride of corresponding amines or carbonate, the amine salt and phosgene reaction are prepared into isocyanide then
Acid esters, when aliphatic, alicyclic isocyanate is prepared, it will usually select amine is prepared into corresponding hydrochlorate and carbonate again first
Carry out photochemical reaction.
British patent GB1162155A is disclosed and generates hydrochlorate in -10-50 DEG C of amine and hydrogen chloride gas salt-forming reaction, molten
The ratio 30 of agent and amine:1-18:1, photochemical reaction is carried out at 120-160 DEG C.British patent GB1086782A is disclosed, in 0-60
DEG C amine generates hydrochlorate with hydrogen chloride gas salt-forming reaction, and the ratio 30 of photochemical reaction, solvent and amine is carried out at 120-128 DEG C:
1-18:1.Though above two method reduces the generation of photochemical reaction byproduct in process thing, because of its course of reaction by improving
Used in solvent ratios it is excessive, solvent evaporation during post processing needs to consume big energy, and too low concentration needs reactor etc.
Equipment size increases, and causes volume efficiency and economic benefit bad.
British patent GB1146664A discloses the amine of 7wt% at 25 DEG C by film reactor and hydrogen chloride into salt, so
Afterwards first in 160 DEG C of phosgenation reactions, the then phosgene reaction at 190 DEG C again.Using film reactor into salt, if liquid film is relatively thin
Idle running rate is low；If liquid film is thicker, hydrogen chloride can not enter liquid film depths, and the hydrochlorate of top layer production within a short period of time
Prevent hydrogen chloride from traveling further into inside liquid film, cannot industrially realize into salt not exclusively.
Chinese patent CN101203488A is disclosed in pressure more than atmospheric pressure 0.01MPa, into salt at 120 DEG C of temperature, can
To reduce the viscosity of hydrochlorate, so as to improve salt-forming conversions rate and space-time yield, amine is converted into the conversion ratio of hydrochlorate and can reach
To 99.8mol%, the yield of the isocyanates obtained after phosgenation reaction is up to 98.10%.Although the patent relies on high temperature solution
Determined into the problem of salt viscosity, but due under high temperature fatty (ring) race's amine with hydrogen chloride gas precursor reactant quickly, amine cladding is serious,
Into salt not exclusively, final phosgenation liquid has substantial amounts of ureogenesis, and easily generates chloro by-product, and separating to the later stage increases difficulty.
Chinese patent CN1045578A is disclosed and is made solvent with ester, and wherein the amount control of solvent is in solvent and amine or its hydrochloric acid
The weight ratio of salt is from 8：1-16：1, at 30 DEG C or less than at a temperature of 30 DEG C, amine carries out cold reaction or into salt with phosgene or hydrogen chloride
Reaction, carries out thermal response with phosgene at 120-170 DEG C and prepares isocyanates, yield 91wt% or so.Although the technology is certain
The generation of chloro by-product is reduced in degree, isocyanates separating-purifying difficulty, but the more traditional benzene of used esters is reduced
Series solvent is on the high side, and economic benefit is bad, it is difficult to realization of industrialization.
Chinese patent CN102070491A is disclosed at 25-35 DEG C, and phenylenedimethylidyne diamidogen is with hydrogen chloride gas into salt
Reaction generation hydrochlorate, hydrochloride concentration 4-6wt% in salt-forming reaction kettle, gained hydrochlorate centrifugal concentrating is to hydrochloride concentration
After 20-30wt% Jing after high pressure, two step of low pressure are photochemical be obtained containing XDI reactant liquor.The patent first exists
Into salt and then concentration in weak solution, hot photochemical reaction after concentration, is carried out, so as to reduce the response time, improve Spatial-temporal Transformation rate, but
It is hydrochlorate viscosity increase after its concentration, is unfavorable for conveying and the stirring in hot photochemical reaction stage mixing in pipeline, industrialization
On be difficult to realize.
Isocyanate production processes are primarily present two class by-products, and one type by-product is amino-compound, aminoacyl
The hydrochlorate of chlorine and chlorination hydrogen evolution, another kind of by-product are that amino acyl chlorides, diamino compounds and isocyanates form urea
Oligomer.If mixing is uneven during into salt hybrid reaction, the high local concentrations of amino-compound are easily caused, so as to
Cause the generation of by-product.Above-mentioned by-product is generally insoluble in Conventional solvents, not only reduces reaction yield, simultaneously because room temperature
It is solid-state down, easily blocks pipeline, therefore, the generation of side reaction is reduced, always phosgenation reactor improves the weight with innovation
Point.EP0699657B1 discloses a kind of coaxial injector；CA2258194A1 discloses a kind of micro structure formula nozzle；
EP1275639B1 discloses a kind of Venturi nozzle；W003045900A1 is disclosed and the board-like anti-of porous distributor is set in a kind of
Answer device；EP1319655B1 discloses a kind of distribution mode of small hole injection gas；CN1310875C discloses one kind in middle equipressure
The plate-type reactor operated under power；US2005113601A1 discloses a kind of pipe reaction with central nozzle and vortex generator
Device.GB1165831A discloses a kind of tubular reactor with stirring；CN101372463A discloses a kind of jet injection reaction
Device；W02008055898A1 discloses a kind of tubular reactor with nozzle；CN101357316A discloses a kind of three pipes cocurrent
Formula reactor.Existing reactor needs the big energy that dissipates, or complex structure, or causes local concentration inconsistent.
CN101623615A discloses a kind of telescopic distributor, it is proposed that the mixing on whole flow area, but due to material point
Enter into several strands, increased control and operation difficulty.
Innovation in terms of the technologic optimization of above-mentioned salt-forming reaction and reactor mixed form can not realize amino with
The conversion completely of hcl reaction.Amino is acid-base neutralization reaction, predominantly mass transfer with the salt-forming reaction process nature of hydrogen chloride
Control, its raw material mixed effect directly determine reaction effect.Especially aliphatic amine activity is higher, in cold reaction or salt-forming reaction
During be comparatively fast easily caused amine salt cladding, cause the conversion ratio of amine relatively low, the unconverted amine being wrapped by is in phosgenation thermal response
Stage can generate the by-products such as substituted urea with the reaction of product isocyanates, cause ultimate yield reduction and product quality to decline.
In order to overcome existing isocyanates into photochemical reaction space-time in the case of amine hydrochlorate low concentration in salt photochemical process
Conversion ratio is low, and under high concentration, amide hydrochloride viscosity is excessive, causes amine incomplete into salt, and side reaction is more, and is difficult conveying etc.
Problem, needs to be improved prior art.
The content of the invention
It is an object of the invention to provide a kind of method for preparing isocyanates, based on into salt phosgenation reaction, is not dropping
In the case of low salt-forming reaction amine hydrochlorate concentration, preliminary salt-forming reaction is carried out using traditional salt-forming reactor, subsequently into
Salt slaking reaction is carried out in salt slaking reaction device, a certain proportion of low-molecular-weight ketone or nitrile are added in hydrochlorate slurry
Solvent, improves the situation that hydrochlorate slurry disperses inequality in traditional halogenated aryl hydrocarbon class atent solvent, makes hydrochlorate slurry microcosmic
Size distribution is more uniform, obtains the hydrochlorate slurry of high conversion rate, even particle size distribution, and then when shortening hot photochemical reaction
Between, the generation of by-product in photochemical process is reduced, final products isocyanates yield and product quality is improved.
In order to realize above goal of the invention, the technical solution adopted in the present invention is as follows:
A kind of method for preparing isocyanates, comprises the steps：
(a) preliminary salt-forming reaction：Amine obtains amine salt acid Jing after inert organic solvents dilution with the preliminary salt-forming reaction of hydrogen chloride
Salt slurry；
B () is into salt slaking reaction：Amine hydrochlorate slurry obtained by step (a) is imported in salt slaking reaction device, while
Polar organic solvent in addition, is passed through hydrogen chloride ripening salt-forming reaction, obtains ripening amine hydrochlorate slurry；
(c) pressurization phosgenation reaction：Ripening amine hydrochlorate slurry obtained by step (b) and phosgene are carried out into pressurization phosgenation anti-
Should, obtain the reactant liquor containing isocyanates；
(d) product purification：Reactant liquor containing isocyanates obtained by step (c) is refining to obtain into isocyanate products.
Isocyanates prepared by the present invention have logical formula (I)：
R(NCO)n(I),
Wherein, n is 2 or 3；R represents aromatic group, aliphatic or alicyclic hydrocarbon radical, preferred aliphat or alicyclic alkyl,
More preferably carbon number is the aliphatic or alicyclic hydrocarbon radical of 4-15；The R is more preferably hexa-methylene, two methylene of isophthalic
Base, terephthalylidene or anti-form-1,4- cyclohexyl；Much further preferably from m-phenylenedimethylim- or terephthalylidene；Most
Preferably m-phenylenedimethylim-；
The isocyanates be preferably m-xylylene diisocyanate and/or terephthalylidene diisocyanate,
Isophorone diisocyanate, hexamethylene diisocyanate, anti-form-1,4- cyclohexylene diisocyanates；More preferably isophthalic two
Methylene diisocyanate or terephthalylidene diisocyanate, more preferably m-xylylene diisocyanate.
In step (a) the of the present invention preliminary salt-forming reaction：
The amine has logical formula (II)：
R(NH2)n(II),
Wherein, R and n are defined as described above, identical with R and n in isocyanates formula prepared by the present invention；N be 2 or
3；R represents aromatic group, aliphatic or alicyclic hydrocarbon radical, preferred aliphat or alicyclic alkyl, and more preferably carbon number is 4-
15 aliphatic or alicyclic hydrocarbon radical；The R is more preferably hexa-methylene, m-phenylenedimethylim-, terephthalylidene, anti-
Formula -1,4- cyclohexyl；Much further preferably from m-phenylenedimethylim- or terephthalylidene；Most preferably m-phenylenedimethylim-.
In the present invention, the amine is preferably meta-xylylenediamine and/or terephthalylidene diamidogen, isophorone two
Amine, hexamethylene diamine, anti-form-1,4- cyclohexanediamine；More preferably meta-xylylenediamine.
Described in the preliminary salt-forming reaction of step (a) of the present invention, inert organic solvents are to be conducive to stablizing for the salt-forming reaction
Property, and be conducive to reacting the atent solvent of each component dissolubility, the inert organic solvents include but is not limited to benzene, toluene, chlorine
In benzene, o-dichlorohenzene (ODCB), paracide, a chlordiphenyl, dimethyl terephthalate ester and diethyl phthalate
One or two or more；The inert organic solvents are preferably o-dichlorohenzene (ODCB).
During amine salt-forming reaction of the present invention, from into the consideration of salt angle, amine is generated with hcl reaction in inert organic solvents
Amine hydrochlorate.
Hydrogen chloride of the present invention is pure hydrogen chloride gas, and the hydrogen chloride with the molar equivalent ratio of the amino of the amine is
1.0-2.5:1, preferably 1.2-2.0:1.In step (a) of the present invention, hydrogen chloride is kept to be more than 1.2 with the equivalent proportion of amino,
The high conversion of amine can be then kept, while equivalent proportion is controlled below 2.0, from the viewpoint of economy, industrially more
Favorably.
Consider industrial production efficiency, in the preliminary salt-forming reaction of step (a) of the present invention, based on amine and inert organic solvents
Gross mass, the input concentration of the amine is 5-30wt%, preferably 10-20wt%.In rapid (a) of the invention, control charging amine
Concentration is more than 5wt%, it is possible to achieve high efficiency；It is below 30wt% to control simultaneously to feed amine concentration, anti-in phosgenation
The problems such as Ying Zhongneng effectively suppresses the side reaction of phosgenation urea and chloride to increase.
Step (a) of the present invention can adopt the reactor with coaxial injector, the reactor with micro structure formula nozzle
Or the various published reactors such as the reactor with Venturi nozzle.
The preliminary salt-forming reaction time of staying of step (a) of the present invention is 100ms-15s, preferred 1-5s.
The temperature of step (a) the of the present invention preliminary salt-forming reaction is 0-30 DEG C.When temperature is higher than 30 DEG C, salt-forming reaction
The cladding of the too fast amine for easily causing, causes the increase of chlorinated impurities；When temperature is 30 DEG C or is less than 30 DEG C, or even near 0 DEG C
The reaction result that can be obtained；Although can also obtain amine hydrochlorate at lower temperatures, disadvantageously, since it is desired that
It is a large amount of to cool down, and salt-forming reaction speed can be corresponding slack-off.Consider miniaturization, the viscosity of hydrochlorate of hydrochlorate particle diameter, with
And the follow-up factor such as with thermal balance during phosgene reaction, therefore, in the present invention, the temperature of the preliminary salt-forming reaction of step (a) is preferred
For 20-25 DEG C.
The concentration of the amine hydrochlorate slurry that step (a) of the present invention obtains is 10-30wt%.
Step (b) of the present invention is described into salt slaking reaction:
As the conversion ratio that amine forms hydrochlorate directly affects the effect of follow-up photochemical reaction, amino conversion is incomplete, trip
From amino can generate the by-product such as substituted urea with the NCO group reaction for generating, reduce yield and affect product quality, therefore,
Present invention particularly provides this is into salt curing step, to guarantee the high conversion of amine.
Present invention firstly provides into salt slaking reaction, the stage of reaction in the published light phosgenation patent into salt from
Do not refer to.Add a certain proportion of middle polarity organic in the amine hydrochlorate slurry obtained to step (a) in step (b) in the present invention
Solvent, can effectively improve dissolubility of the amine hydrochlorate in inert organic solvents, improve amine hydrochlorate in traditional halogenated aryl hydrocarbon
The situation of skewness in class atent solvent so that cladding free amine group amine hydrochlorate granule be partly dissolved it is broken, by inside
Free amine group is discharged, and further reacts generation amine hydrochlorate, ripening salt-forming reaction, it is ensured that free amino with hydrogen chloride gas
Hydrochlorate is converted into greatest extent.
In described in step (b) of the present invention, polar organic solvent should be inert, chosen pole relative to reaction system
Property organic solvent boiling point should be less than atent solvent used by salt-forming reaction boiling point.
In described in step (b) of the present invention, polar organic solvent is low-molecular-weight ketone or the one kind or many in nitrile solvents
Kind, preferred boiling point for 50-100 DEG C ketone or nitrile solvents in one or more, more preferably acetone, butanone and acetonitrile
In one or two or three kinds.
In the present invention, it is based on step that step (b) adds the consumption of the middle polar organic solvent in hydrochlorate slurry
The 5-20wt%, preferred 10-15wt% of a amine hydrochlorate slurry gross mass that () obtains.The consumption of the middle polar organic solvent
It is during less than 5wt%, unobvious to the polarization state improvement result of original dispersion, it is impossible to realize improving hydrochloric acid salt particle molten
Dissolubility in agent, does not have the effect for promoting into salt ripening, when the consumption of middle polar organic solvent is higher than 20wt%, hydrochlorate
Granule dissolubility in a solvent there is no longer and significantly improve, and cross the addition of solvent at high proportion, and will certainly increase causes subsequently
Separating difficulty simultaneously increases separating energy consumption.
Step (b) reaction time of the present invention is 1-15min, preferred 5-10min；It is passed through amount and the amine salt acid of hydrogen chloride
The molar equivalent ratio of the amino of salt is 0.6-1.0:1.
In the present invention step (b) into salt slaking reaction reactor be tank reactor, the inside of the tank reactor
Liquid slurry disperser of the core component for hourglass shape.
In the present invention, the stirring paddle of the tank reactor is located at the axle center of tank reactor, and the stirring paddle is for radially
Stirring paddle based on stream, can open vane wheel oar, four oblique leaves for six straight leaves and open vane wheel oar or straight leaf disc vane wheel oar etc. and can carry
For high shear and systemic circulation ability radial flow based on stirring paddle form；The stirring paddle can be one group, or it is many
Group；The stirring paddle is via shaft in the dynamic lower rotation at a high speed of outside motor belt motor, rotating speed 500-1000rpm, it is ensured that in disperser
In high speed turbulence state, the radial thrust that stirring paddle brings gets rid of hydrochlorate slurry to hourglass shape liquid slurry point to hydrochlorate slurry
Scattered device.
In the present invention, the liquid slurry disperser main body of the hourglass shape is cylinder of the hourglass shape with bottom, hourglass shape
The area equation of the upper and lower end face of shape cylinder or；It is preferred that the hourglass shape liquid slurry disperser of upper and lower end face area equation；Institute
State the 1/4-1/2, preferred 1/3-1/2 of the height for tank reactor height of hourglass shape liquid slurry disperser；The hourglass shape
1/6-1/5 of the distance of liquid slurry disperser lower surface and tank reactor bottom surface for tank reactor height；The autoclave
The stirring paddle of reactor is located at hourglass shape liquid slurry disperser axle center, stirrer paddle and hourglass shape liquid slurry disperser
1/4-1/3 of the lower surface distance for liquid slurry disperser height；The cross section minimum of the hourglass shape liquid slurry disperser
1/3-2/3 of the circular diameter for hourglass shape liquid slurry disperser lower surface circular diameter；Stirring paddle radical length is hourglass shape liquid
The 2/3-5/6 that pulp stock disperser lower surface circular diameter is；The 3/4-5/4 of a diameter of lower surface in hourglass shape cylinder upper surface；Hourglass
The 2/5-3/5 of a diameter of reactor diameter in shape cylinder lower surface.
In the present invention, the hourglass shape liquid slurry disperser is heated using outer coils, and outer coils can be adopted
With electrical heating, it would however also be possible to employ circulator bath or circulation oil bath heating.Maintain slurry in the hourglass shape liquid slurry disperser
Temperature 60-90 DEG C, at this temperature, the amine hydrochlorate slurry can maintain low viscosity, keep preferable mobility, while plus
Thermal process can promote the hydrochlorate for coating free ammonia partial crushing under thermal stress effect, and the free ammonia of cladding is partly discharged
Out；And temperature less than 60 DEG C then hydrochlorate slurry viscosity it is larger, poor fluidity；Temperature can cause hydrochlorate higher than 90 DEG C in addition
It is unstable, cohesion is susceptible to, formation is difficult to broken bulk granule, affects thermal reaction rate.
In the present invention, the cylinder of the liquid slurry disperser of hourglass shape described in step (b) is porous cylinder, cylinder arrangement
There is star shape discharging opening.The outer corners angle of the star shape is to be less than or equal to 60 degree more than or equal to 15 degree, it is ensured that liquid
Somaplasm material can be subject to the shear action of discharging opening edges and corners, discharging opening star shape to be including but not limited to when spraying from discharging opening
One or two or more in triangle star, corner star, pentalpha, hexagram, heptangle star and anistree star etc..
When more than 60 degree, then slurry passes through the liquid outlet opening corner angle angle, shear action deficiency causes shear effect poor, corner angle angle
Then slurry can be caused to not easily pass through edges and corners because circulating face is narrow when degree is less than 15 degree, easily form material dead band.
In the present invention, as axial direction height is different, the hourglass shape liquid slurry disperser cross-sectional area is also different,
Its cylinder top discharge mouth percent opening, perforate size and hole shape etc. are also differed.The overall perforate of cylinder described in step (b)
Rate is 50-75%；Whole cylinder height is preferably based on, the cylinder upper surface of the liquid slurry disperser of the hourglass shape is arrived
Cylinder percent opening apart from upper surface 1/3 in is 55-70%, based on whole cylinder height；Distance is arrived apart from upper surface 1/3
The percent opening of the cylinder between lower surface 1/3 is 50-60%, based on whole cylinder height；Cylinder lower surface is to apart from lower surface
Cylinder percent opening in 1/3 distance is 60-75%, based on whole cylinder height.The cylinder entirety percent opening is less than 50% meeting
Liquid slurry is caused to flow out discharge area inadequate, it is impossible to ensure that slurry smoothly flows out in liquid slurry disperser, percent opening is higher than
75% can cause slurry to flow out, and discharge area is excessive, and the suffered shearing of slurry is not enough, reduces gas-liquid mixed effect.
In the present invention, by taking laterally zygomorphic hourglass shape liquid slurry disperser as an example：The amine hydrochlorate slurry that step (a) is obtained
Expect to be imported in the internal core part liquid pulp stock disperser of tank reactor by liquid inlet opening, the design of hourglass shape can be protected
, in its internal turbulence, under centrifugal force and self gravitation dual function, the hydrochloric acid salt particle of large-size is more for card liquid slurry
Hourglass bottom is distributed in easily, secondly size hydrochloric acid salt particle placed in the middle is mainly distributed on upper and lower both sides at hourglass axial centre,
Hydrochlorate pulp particle size in hourglass top is minimum.
Because of the special shape of the hourglass shape liquid slurry disperser in the present invention, the salt of different scale in hydrochlorate slurry
Hydrochlorate granule has specific distribution on axially different height, therefore, hourglass shape liquid slurry disperser liquid outlet opening star shape
The size of shape also accordingly should be adjusted.Based on whole cylinder height, upper surface discharges to the star between upper surface 1/3
The size of the star shape of mouth is measured with its circumscribed circle, a diameter of 150-300 μm of its circumscribed circle；Should in the range of material for
The grain less hydrochlorate slurry of granularity, thus liquid outlet opening can to arrange size larger, be easy to increase material circulation, improve
The production capacity of equipment.Based on whole cylinder height, star of the cylinder lower surface to the star discharging opening between lower surface 1/3
The size of shape shape is measured with its circumscribed circle, and its circumscribed circle diameter is 50-150 μm；In the range of being somebody's turn to do, material particles degree is larger, then should
Position discharging opening arranges size should be less, it can be ensured that is sheared by enough during hydrochlorate slurry flows, by hydrochloric acid salt particle
Size is broken to be reduced, while the free amine group coated by hydrochlorate is discharged completely.Based on whole cylinder height, apart from upper
End face 1/3 is measured to the size of the star shape of the star discharging opening between lower surface 1/3 with its circumscribed circle, its circumscribed circle
A diameter of 80-200 μm；Material in the range of being somebody's turn to do is the moderate hydrochlorate slurry of grain graininess.
In the present invention, based on whole cylinder height, cylinder lower surface to the star discharging opening between lower surface 1/4 is
Triangle star or corner star；Discharging opening in the range of being somebody's turn to do also should ensure that hourglass shape in addition to the shearing of hydrochloric acid salt particle is completed
Without dead band in liquid slurry disperser, i.e., the disperser can be left into into salt into the material in the liquid slurry disperser
Slaking reaction kettle lower end.
The present invention, the dry hydrogen chloride gas Jing gas-phase feed pipes introduce into salt slaking reaction bottom portion, by one
Porous gas distributing disc generates amine with the free amine group reaction coated by hydrochlorate for discharging into into salt slaking reaction kettle
Hydrochlorate, completes the ripening of salification process.The porous gas distributing disc is located inside slaking reaction kettle, and a diameter of reactor is straight
The 3/5-4/5 in footpath, end face distance hourglass shape liquid slurry disperser lower surface distance is the 1/12-1/ of reactor height thereon
10, the diameter dimension of the miniature circular hole of the porous gas distributing disc is 5mm-2cm, and percent opening is 60-80%.Percent opening is less than
60% can cause gas outlet position very few, and gas deployment conditions are bad, and percent opening can cause gas outlet section higher than 80%
Product is excessive, and under identical ventilation, gas flow rate is relatively low, reduces gas-liquid mixed effect.
In adopting the inventive method, internal core part is carried out for the tank reactor of the liquid slurry disperser of hourglass shape
It is into salt slaking reaction, when the amine hydrochlorate slurry concentration obtained in step (a) is 10wt%, anti-into salt ripening in step (b)
The ripening amine hydrochlorate slurry obtained after ripening in kettle is answered, the viscosity at 30 DEG C is below 1500mPa.s.And using tradition into
Salt method, in 10wt%, the viscosity of hydrochlorate slurry rises to 8000- at 30 DEG C to amide hydrochloride concentration
20000mPa.s.According to general knowledge, when hydrochlorate slurry viscosity is higher than 5000mPa.s, pipeline in production process, is easily caused to block,
The hydrochlorate slurry prepared by the method that the present invention is provided is not easily caused pipeline blocking, process units operation in process of production
Stability obtains larger raising.
In addition, in the conditions of the invention, the particle diameter of hydrochloric acid salt particle in hydrochlorate slurry can be suppressed to increase, as salt
When in reactor, amide hydrochloride concentration remains 10wt%, the number average bead diameter of hydrochloric acid salt particle is 5-20 μm；Using tradition into
Salt method, when amide hydrochloride concentration reaches 10wt% in a kettle., in solution, the mean diameter of particle is 80-150 μm,
Larger particle size is unfavorable in the phosgenation reaction described in step (c) is carried out, and hydrochlorate particle size conference causes
The hydrochlorate particle surface product of the amount of same substance is little, is unfavorable for the haptoreaction of hydrochlorate and phosgene, by present invention offer
The hydrochlorate particle diameter for preparing of method it is little, the hydrochlorate particle surface of the amount of same substance product is big, is conducive to hydrochlorate and phosgene
Haptoreaction.
In pressurization phosgenation reaction described in step (c) of the present invention：
In the present invention, the pressurization phosgenation reaction, also referred to as high pressure phosgenation reaction, in 0.1-1.5MPa, preferably
Operate under the absolute pressure of 0.2-0.6MPa.When pressure is less than 0.2MPa, phosgenation reaction speed is slower, and when being higher than 0.6MPa
Equipment and operation are required higher.
Due to the characteristic of the phosgenation reaction of amine hydrochlorate, according to generally accepted viewpoint, the phosgenation of amine hydrochlorate is non-
Often slow and reaction is divided into two steps and carries out：
The first step, amine hydrochlorate generate carbamyl chloride with phosgene reaction；
Second step, carbamyl chloride decompose generation isocyanates and release hydrogen chloride simultaneously.
Preferably, two steps of the pressurization phosgenation reaction of heretofore described amine hydrochlorate are under the following conditions
Carry out：
The first step, is carried out under relatively high pressure condition, and the absolute pressure of reaction is preferably 0.4-0.6MPa；
Second step, is carried out under relatively low pressure condition, and the absolute pressure of reaction is preferably 0.2-0.4MPa.
Carbamyl chloride is dissociated into isocyanates and hydrogen chloride, is pressure dependence type balancing response.The present invention is by appropriate
The pressure for reducing compressive reaction can be such that the reaction offsets to product isocyanates side.Because carbamyl chloride decomposes not require to appoint
What phosgene, in solution, a small amount of hydrochlorate of remaining also only needs the feature of a small amount of phosgene, low-pressure to cause phosgene in phosgenation operation
Hold-up is low, and this is also advantageous from terms of security standpoint.
In the present invention, the reaction temperature of step (c) the pressurization phosgenation reaction is 120-170 DEG C, preferred temperature
It is 140-150 DEG C.When reaction temperature is less than 120 DEG C, photochemical reaction overlong time then can be excessive because of side reaction higher than 170 DEG C
Yield is caused to decline.In the present invention, the heating embodiment of the reactor of the pressurization phosgenation reaction need to be passed through according to phosgene
And the temperature caused by phosgenation reaction reduces being adjusted.
In the present invention, the type of reactor of step (c) the pressurization phosgenation reaction can select tubular reactor, stirring
Container and miscellaneous equipment.
In the present invention, the mean residence time of step (c) the pressurization phosgenation reaction is 1-600 minutes, preferably average
Minute time of staying 30-300, more preferably 60-180 minutes.
The phosgene that step (c) the pressurization phosgenation is passed through is 1.2 with the mol ratio of amino in amine hydrochlorate:1-10:1,
It is preferred that 1.5-8：1.
In the present invention, the phosgene of step (c) the pressurization phosgenation reaction is led in the form of pure phosgene or phosgene solution
Enter, the solvent of the phosgene solution is selected from benzene, toluene, chlorobenzene, o-dichlorohenzene, paracide, a chlordiphenyl, p-phthalic acid two
One or two or more in Arrcostab and diethyl phthalate.Phosgene in phosgene solution accounts for the 10- of solvent quality
30wt%.
Product purification described in step (d) of the present invention：
Product purification of the present invention need to remove unreacted phosgene, hydrogen chloride, and solvent, tar etc. is evaporated off.
In the present invention, product purification needs one or more rectifying columns as the equipment of separation and purification of products, product purification
The removing of removing, inert organic solvents including hydrogen chloride gas in reactant liquor and phosgene, reaction heavy constituent by-product (are commonly called as Jiao
Oil) removing and the removing of light component impurity that is close to of boiling point and product etc..
The isocyanate products purity prepared in the present invention reaches 99.90wt%-99.95wt%, and product color number can reach
0-5Hazen, the hydrolyzable chloride content in product are 0-10ppm, and chloride content is 0-100ppm.
In the present invention, the conversion ratio of amine can reach 99.0-99.9mol%.And tradition is in salt photochemical process, in reactor
When middle amide hydrochloride concentration reaches 1Owt%, the salt-forming conversions rate of amine is 95.0-97.0mol%, when amine salt in reactor
When acid salt solution concentration reaches 15wt%, the salt-forming conversions rate of amine is only 90.0-94.5mol%.Salt-forming conversions rate Gao Ze of amine
The high income of isocyanates, and the generation of by-product can be suppressed.
The beneficial effects of the present invention is：
Adopt internal core part first for hourglass shape liquid slurry disperser tank reactor as into salt ripening
Reactor, the shear action of the star discharging opening being distributed on the cylinder by hourglass shape liquid slurry disperser, promote hydrochloric acid
The crushing again of salt reduces the effect of hydrochlorate particle diameter and viscosity.
Into in salt maturing process, add appropriate middle polar organic solvent to effectively improve the dissolving in a solvent of hydrochloric acid salt particle
Degree, plays a part of to promote into salt ripening.
The isocyanate products that the present invention is prepared have purity high, and color number is low, and hydrolysis chlorine, chloride content are low excellent
Point.
Description of the drawings：
It is illustrating into salt slaking reaction kettle for laterally zygomorphic hourglass shape liquid slurry disperser that Fig. 1 is internal core part
Figure
1 gas-phase feed pipe
2 first liquid phase feeding pipes
3 second liquid phase feed pipes
4 gaseous phase outlets
5 hourglass shape liquid slurry dispersers
6 stirring paddles
7 porous gas distributing discs
8 leakage fluid drams
Fig. 2 is 2 laterally zygomorphic hourglass shape liquid slurry disperser center Longitudinal cross section schematic of embodiment
The outer coil pipe of 9 electrical heating
10 star liquid slurry discharging openings
Specific embodiment
The following examples will be further described to method provided by the present invention, but the invention is not restricted to listed
The embodiment for going out, should also be included in other any known changes in interest field of the presently claimed invention.
Purity test instrument and condition：Shimadzu GC-2010, pillar：DB-5 30 × 0.25mm × 0.25 μm sample size：1μ
L, gasify room temperature：260 DEG C, column flow：1mL/min, split ratio：50:1, column temperature：50 DEG C, 2min is kept, it is fast with 5 DEG C/min
Rate is warming up to 80 DEG C, keeps 5min, with 20 DEG C/min ramps to 280 DEG C, keeps 10min, detector temperature：300℃
Particle diameter testing standard and INSTRUMENT MODEL：Rise-2002 type wet method laser diffraction formula Particle Size Analyzers are in acetonitrile solution
The middle particle diameter for determining hydrochloric acid salt particle
Color number is tested：2250 type color instrument of Lovibond Nessleriser
Viscosity test：Brookfield R/S flow graphs
Chloride content testing standard：GB12009.1-89
Hydrolysis chlorine testing standard：GB12009.2-89
As shown in Figure 1：Hydrochlorate slurry obtained in the preliminary salt-forming reactions of Jing is by entering into salt slaking reaction the first liquid phase of kettle
Expects pipe 2 is incorporated in hourglass shape liquid slurry disperser 5, and middle polar solvent introduces hourglass shape liquid by second liquid phase feed pipe 3
In pulp stock disperser 5, hydrogen chloride gas Jing gas-phase feeds pipe 1 is introduced in gas distributing disc 7, and the agitated oar 6 of hydrochlorate slurry is high
Hourglass shape liquid slurry disperser 5 is left after being sheared by liquid slurry disperser star discharging opening again after speed shearing propulsion,
Hydrochlorate slurry after slaking reaction is completed squeezes into pressurization phosgenation reaction kettle, excessive gas in whole process by leakage fluid dram 8
Jing gaseous phase outlets 4 are discharged.
Embodiment 1
Using be blown into pipe with injection reactor, phosgene and the autoclave that stirs as step a consersion unit, volume is
10 liters.In raw material tank, (feeding total amine concentration is for input 817g (6mol) MXDPs and 7354g o-dichlorohenzenes
MXDP solution (or referred to as reactant liquor) is formed 10wt%).External cooling method is adopted to keep reacting liquid temperature for 20 DEG C.
Hydrogen chloride gas are passed in the nozzle of injection reactor by high-pressure pump, hydrogen chloride is passed through speed 8L/min, while using
Raw material pump spurts into MXDP solution with the nozzle that the speed of 158g/min begins through injection reactor, while opening
The stirring for opening reactor carries out preliminary salt-forming reaction.
The present embodiment is used to be disperseed into salt slaking reaction kettle using the hourglass shape liquid slurry of upper and lower end face area equation
Device, the height of the hourglass shape liquid slurry disperser is the 1/4 of tank reactor height, the hourglass shape liquid slurry dispersion
Device lower surface is the 1/5 of tank reactor height with the distance of tank reactor bottom surface, and stirring paddle is divided with hourglass shape liquid slurry
Scattered device lower surface distance is the 1/4 of liquid slurry disperser height, the cross section minimum of the hourglass shape liquid slurry disperser
Circular diameter for hourglass shape liquid slurry disperser lower surface circular diameter 1/3, stirring paddle radical length are hourglass shape liquid slurry
The 2/3 of disperser lower surface circular diameter, the 2/5 of a diameter of reactor diameter in hourglass shape cylinder lower surface.It is high based on whole cylinder
Degree, the cylinder upper surface of the liquid slurry disperser of the hourglass shape to the cylinder percent opening apart from upper surface 1/3 in is
55%；Percent opening apart from upper surface 1/3 to the cylinder between lower surface 1/3 is 50%；Cylinder lower surface is under distance
Cylinder percent opening of the end face 1/3 in is 60%.The star shape outer corners angle is 15 degree, the outlet star shape
Shape is triangle star.
Hydrochlorate slurry obtained in initial reactor is by introducing slush pulp into salt slaking reaction the first liquid phase feeding of kettle pipe 2
In material disperser 5, slurry feed rate is 100g/min, and acetone introduces liquid slurry disperser 5 by second liquid phase feed pipe 3
In, charging rate is 10g/min, and liquid slurry disperser 5 is 70 using outer coil pipe electric tracing, maintenance hydrochlorate slurry temperature
DEG C, after agitated 6 high speed shear of the oar propulsion of hydrochlorate slurry after the star discharging opening shearing on liquid slurry disperser surface
Into into salt slaking reaction kettle, while hydrogen chloride gas Jing gas-phase feeds pipe 1 is introduced in Gas distribution disk 7, hydrogen chloride gas Jing
Into into salt slaking reaction kettle, it is 4L/min that hydrogen chloride is passed through speed to Gas distribution panel surface aperture, stops reaction 10min, will
MXDP hydrochlorate slurry squeezes into pressurization phosgenation reaction kettle, excessive gas Jing gas in whole process by outlet 8
Mutually outlet 4 is discharged.
Wherein in preliminary salt-forming reaction operation, hydrogen chloride gas and the equivalent proportion of phenylenedimethylidyne diamidogen amino are 1.5:
1, from sampling into salt ripening kettle outlet after terminating into salt, hydrochlorate is determined in acetonitrile solution using laser diffraction formula particle size analyzer
The particle diameter of particle, it is 15um that Jing determines the number average bead diameter of hydrochloric acid salt particle.Then phosgenation reaction kettle is warming up to into 145 DEG C, is used
Phosgene is blown into pipe and is blown into phosgene with 35g/min, and reaction absolute pressure is maintained at 0.5MPa, reacts 1.5h, then will be reaction absolute
Pressure is down to 0.1Mpa, and the speed that is passed through of phosgene changes 5g/min, reacts 2h, after reaction terminates, by being blown into nitrogen into system,
Thus unreacted phosgene and hydrogen chloride gas are removed.The phosgenation liquid of gained is carried out into desolventizing, rectification obtains 1128g and (receives
Rate is 99.9mol%) XDI, product data refer to table 1.
Embodiment 2
Using tank reactor same as Example 1.817g (6mol) MXDP is put in raw material tank
MXDP solution (or referred to as reactant liquor) is formed with 7354g o-dichlorohenzenes (the total amine concentration of charging is 10wt%).Adopt
It is 20 DEG C that reacting liquid temperature is kept with external cooling method.Hydrogen chloride gas are passed into by high-pressure pump for the nozzle of injection reactor
In, hydrogen chloride is passed through speed 8L/min, while begin through the spray of injection reactor with raw material pump with the speed of 158g/min
Mouth spurts into MXDP solution, while the stirring for opening reactor carries out preliminary salt-forming reaction.
The present embodiment is used to be disperseed into salt slaking reaction kettle using the hourglass shape liquid slurry of upper and lower end face area equation
Device, the height of the hourglass shape liquid slurry disperser is the 1/3 of tank reactor height, the hourglass shape liquid slurry dispersion
Device lower surface is the 1/6 of tank reactor height with the distance of tank reactor bottom surface, and stirring paddle is divided with hourglass shape liquid slurry
Scattered device lower surface distance is the 1/3 of liquid slurry disperser height, the cross section minimum of the hourglass shape liquid slurry disperser
Circular diameter for hourglass shape liquid slurry disperser lower surface circular diameter 1/2, stirring paddle radical length are hourglass shape liquid slurry
The 5/6 of disperser lower surface circular diameter, the 3/5 of a diameter of reactor diameter in hourglass shape cylinder lower surface.It is high based on whole cylinder
Degree, the cylinder upper surface of the liquid slurry disperser of the hourglass shape to the cylinder percent opening apart from upper surface 1/3 in is
65%；Percent opening apart from upper surface 1/3 to the cylinder between lower surface 1/3 is 55%；Cylinder lower surface is under distance
Cylinder percent opening of the end face 1/3 in is 70%.The star shape outer corners angle is 40 degree, the outlet star shape
Shape is corner star.
Hydrochlorate slurry obtained in initial reactor is by introducing slush pulp into salt slaking reaction the first liquid phase feeding of kettle pipe 2
In material disperser 5, slurry feed rate is 100g/min, and acetonitrile introduces liquid slurry disperser 5 by second liquid phase feed pipe 3
In, charging rate is 10g/min, and liquid slurry disperser 5 is 70 using outer coil pipe electric tracing, maintenance hydrochlorate slurry temperature
DEG C, after agitated 6 high speed shear of the oar propulsion of hydrochlorate slurry after the star discharging opening shearing on liquid slurry disperser surface
Into into salt slaking reaction kettle, while hydrogen chloride gas Jing gas-phase feeds pipe 1 is introduced in Gas distribution disk 7, hydrogen chloride gas Jing
Into into salt slaking reaction kettle, it is 4L/min that hydrogen chloride is passed through speed to Gas distribution panel surface aperture, stops reaction 10min, will
MXDP hydrochlorate slurry squeezes into pressurization phosgenation reaction kettle, excessive gas Jing gas in whole process by outlet 8
Mutually outlet 4 is discharged.
Wherein in preliminary salt-forming reaction operation, hydrogen chloride gas and the equivalent proportion of phenylenedimethylidyne diamidogen amino are 1.5:
1, from sampling into salt ripening kettle outlet after terminating into salt, hydrochlorate is determined in acetonitrile solution using laser diffraction formula particle size analyzer
The particle diameter of particle, it is 18um that Jing determines the number average bead diameter of hydrochloric acid salt particle.Then phosgenation reaction kettle is warming up to into 145 DEG C, is used
Phosgene is blown into pipe and is blown into phosgene with 35g/min, and reaction absolute pressure is maintained at 0.5MPa, reacts 1.5h, then will be reaction absolute
Pressure is down to 0.1Mpa, and the speed that is passed through of phosgene changes 5g/min, reacts 2h, after reaction terminates, by being blown into nitrogen into system,
Thus unreacted phosgene and hydrogen chloride gas are removed.The phosgenation liquid of gained is carried out into desolventizing, rectification obtains 1127g and (receives
Rate is 99.8mol%) XDI, product data refer to table 1.
Embodiment 3
Using tank reactor same as Example 1.1225g (9mol) MXDP is put in raw material tank
MXDP solution (or referred to as reactant liquor) is formed with 6946g o-dichlorohenzenes (the total amine concentration of charging is 15wt%).Adopt
It is 20 DEG C that reacting liquid temperature is kept with external cooling method.Hydrogen chloride gas are passed into by high-pressure pump for the nozzle of injection reactor
In, hydrogen chloride is passed through speed 12L/min, while begin through the spray of injection reactor with raw material pump with the speed of 158g/min
Mouth spurts into MXDP solution, while the stirring for opening reactor carries out preliminary salt-forming reaction.
The present embodiment is used to be divided into salt slaking reaction kettle using the unequal hourglass shape liquid slurry of upper and lower end face area
Scattered device, the height of the hourglass shape liquid slurry disperser is the 1/3 of tank reactor height, the hourglass shape liquid slurry point
The distance of scattered device lower surface and tank reactor bottom surface for tank reactor height 1/6, stirring paddle and hourglass shape liquid slurry
Disperser lower surface distance is the 1/3 of liquid slurry disperser height, and the hourglass shape liquid slurry disperser is cross section most
Axis of small circle for hourglass shape liquid slurry disperser lower surface circular diameter 1/2, stirring paddle radical length are hourglass shape slush pulp
The 5/6, the 3/4 of a diameter of lower surface diameter in hourglass shape cylinder upper surface of material disperser lower surface circular diameter, under hourglass shape cylinder
End face diameter for reactor diameter 3/5.Based on whole cylinder height, on the cylinder of the liquid slurry disperser of the hourglass shape
End face to the cylinder percent opening apart from upper surface 1/3 in be 65%；Apart from upper surface 1/3 between lower surface 1/3
Cylinder percent opening be 55%；Cylinder lower surface to the cylinder percent opening apart from lower surface 1/3 in be 70%.The star
Shape shape outer corners angle is 40 degree, and the outlet star shape is corner star.
Hydrochlorate slurry obtained in initial reactor is by introducing slush pulp into salt slaking reaction the first liquid phase feeding of kettle pipe 2
In material disperser 5, slurry feed rate is 100g/min, and butanone introduces liquid slurry disperser 5 by second liquid phase feed pipe 3
In, charging rate is 10g/min, and liquid slurry disperser 5 is 80 using outer coil pipe electric tracing, maintenance hydrochlorate slurry temperature
DEG C, after agitated 6 high speed shear of the oar propulsion of hydrochlorate slurry after the star discharging opening shearing on liquid slurry disperser surface
Into into salt slaking reaction kettle, while hydrogen chloride gas Jing gas-phase feeds pipe 1 is introduced in Gas distribution disk 7, hydrogen chloride gas Jing
Into into salt slaking reaction kettle, it is 6L/min that hydrogen chloride is passed through speed to Gas distribution panel surface aperture, stops reaction 10min, will
MXDP hydrochlorate slurry squeezes into pressurization phosgenation reaction kettle, excessive gas Jing gas in whole process by outlet 8
Mutually outlet 4 is discharged.
Wherein in preliminary salt-forming reaction operation, hydrogen chloride gas and the equivalent proportion of phenylenedimethylidyne diamidogen amino are 1.5:
1, from sampling into salt ripening kettle outlet after terminating into salt, hydrochlorate is determined in acetonitrile solution using laser diffraction formula particle size analyzer
The particle diameter of particle, it is 20um that Jing determines the number average bead diameter of hydrochloric acid salt particle.Then phosgenation reaction kettle is warming up to into 145 DEG C, is used
Phosgene is blown into pipe and is blown into phosgene with 53g/min, and reaction absolute pressure is maintained at 0.5MPa, reacts 1.5 hours, then will be reaction exhausted
0.1Mpa is down to pressure, the speed that is passed through of phosgene changes 7.5g/min, reacts 2h, after reaction terminates, by being blown into into system
Nitrogen, thus removes unreacted phosgene and hydrogen chloride gas.The phosgenation liquid of gained is carried out into desolventizing, rectification is obtained
1685g (yield is 99.6mol%) XDI, product data refer to table 1.
Embodiment 4
Using tank reactor same as Example 1.1225g (9mol) MXDP is put in raw material tank
MXDP solution (or referred to as reactant liquor) is formed with 6946g o-dichlorohenzenes (the total amine concentration of charging is 15wt%).Adopt
It is 20 DEG C that reacting liquid temperature is kept with external cooling method.Hydrogen chloride gas are passed into by high-pressure pump for the nozzle of injection reactor
In, hydrogen chloride is passed through speed 12L/min, while begin through the spray of injection reactor with raw material pump with the speed of 158g/min
Mouth spurts into MXDP solution, while the stirring for opening reactor carries out preliminary salt-forming reaction.
The present embodiment is used to be divided into salt slaking reaction kettle using the unequal hourglass shape liquid slurry of upper and lower end face area
Scattered device, the height of the hourglass shape liquid slurry disperser is the 1/2 of tank reactor height, the hourglass shape liquid slurry point
The distance of scattered device lower surface and tank reactor bottom surface for tank reactor height 1/6, stirring paddle and hourglass shape liquid slurry
Disperser lower surface distance is the 1/3 of liquid slurry disperser height, and the hourglass shape liquid slurry disperser is cross section most
Axis of small circle for hourglass shape liquid slurry disperser lower surface circular diameter 1/2, stirring paddle radical length are hourglass shape slush pulp
The 5/6, the 5/4 of a diameter of lower surface diameter in hourglass shape cylinder upper surface of material disperser lower surface circular diameter, under hourglass shape cylinder
End face diameter for reactor diameter 3/5.The cylinder upper surface of the liquid slurry disperser of the hourglass shape is to apart from upper surface
Cylinder percent opening in 1/3 distance is 70%, based on whole cylinder height；Apart from upper surface 1/3 between lower surface 1/3
Cylinder percent opening be 60%, based on whole cylinder height；Open to the cylinder apart from lower surface 1/3 in cylinder lower surface
Porosity is 75%, based on whole cylinder height.The star shape outer corners angle is 60 degree, and the outlet star shape is
Anistree star.
Hydrochlorate slurry obtained in initial reactor is by introducing slush pulp into salt slaking reaction the first liquid phase feeding of kettle pipe 2
In material disperser 5, slurry feed rate is 100g/min, acetone, acetonitrile, butanone mol ratio 1；1:1 mixed liquor is by the second liquid
Phase feed pipe 3 is introduced in liquid slurry disperser 5, and charging rate is 10g/min, and liquid slurry disperser 5 is using outer coil pipe electricity
Heat tracing, maintains hydrochlorate slurry temperature to be 80 DEG C, by liquid slurry point after agitated 6 high speed shear of the oar propulsion of hydrochlorate slurry
Into into salt slaking reaction kettle after the star discharging opening shearing on scattered device surface, while hydrogen chloride gas Jing gas-phase feeds pipe 1 is introduced
In Gas distribution disk 7, into into salt slaking reaction kettle, hydrogen chloride is passed through speed to hydrogen chloride gas Jing Gas distribution panel surface apertures
For 6L/min, reaction 10min is stopped, MXDP hydrochlorate slurry is squeezed into into pressurization phosgenation reaction by outlet 8
Kettle, in whole process, excessive gas Jing gaseous phase outlets 4 are discharged.
Wherein in preliminary salt-forming reaction operation, hydrogen chloride gas and the equivalent proportion of phenylenedimethylidyne diamidogen amino are 1.5:
1, from sampling into salt ripening kettle outlet after terminating into salt, hydrochlorate is determined in acetonitrile solution using laser diffraction formula particle size analyzer
The particle diameter of particle, it is 22um that Jing determines the number average bead diameter of hydrochloric acid salt particle.Then phosgenation reaction kettle is warming up to into 145 DEG C, is used
Phosgene is blown into pipe and is blown into phosgene with 53g/min, and reaction absolute pressure is maintained at 0.5MPa, reacts 1.5 hours, then will be reaction exhausted
0.1Mpa is down to pressure, the speed that is passed through of phosgene changes 7.5g/min, reacts 2h, after reaction terminates, by being blown into into system
Nitrogen, thus removes unreacted phosgene and hydrogen chloride gas.The phosgenation liquid of gained is carried out into desolventizing, rectification is obtained
1683g (yield is 99.5mol%) XDI, product data refer to table 1.
Comparative example 1
The autoclave of pipe and stirring is blown into as consersion unit using with injection reactor, phosgene, volume is 10 liters.
817g (6mol) MXDPs are put in raw material tank and 7354g o-dichlorohenzenes (the total amine concentration of charging is 10wt%) are formed
MXDP solution (or referred to as reactant liquor).External cooling method is adopted to keep reacting liquid temperature for 20 DEG C.By high-pressure pump
Hydrogen chloride gas are passed in the nozzle of injection reactor, hydrogen chloride is passed through speed 8L/min, at the same with raw material pump with
The speed of 158g/min begins through the nozzle of injection reactor and spurts into MXDP solution, while opening reactor
Stirring, wherein the equivalent proportion of hydrogen chloride gas and phenylenedimethylidyne diamidogen amino is 1.5 in salt-forming reaction operation:1.Into salt
After end, the particle diameter of hydrochloric acid salt particle is determined using laser diffraction formula particle size analyzer in acetonitrile solution, and Jing determines hydrochloric acid salt particle
Number average bead diameter be 60um, phosgenation reaction kettle is warming up to into 145 DEG C then, is entered pipe with light air-blowing and phosgene is blown into 35g/min,
Reaction absolute pressure is maintained at 0.5MPa, reacts 1.5 hours, then reaction is carried out under absolute pressure 0.1Mpa, phosgene
It is 5g/min to be passed through speed, reacts 2h, after reaction terminates, by nitrogen is blown into into system, thus removes unreacted phosgene
And hydrogen chloride gas.The phosgenation liquid of gained is carried out into desolventizing, rectification obtains 1106g (yield is 95.0mol%) isophthalic two
Methylene diisocyanate, product data refer to table 1.
Comparative example 2
The autoclave of pipe and stirring is blown into as consersion unit using with injection reactor, phosgene, volume is 10 liters.
1225g (9mol) MXDPs and 6946g o-dichlorohenzenes (the total amine concentration of charging is 15wt%) shape are put in raw material tank
Into MXDP solution (or referred to as reactant liquor).External cooling method is adopted to keep reacting liquid temperature for 20 DEG C.By high pressure
Pump is passed into hydrogen chloride gas in the nozzle of injection reactor, and hydrogen chloride is passed through speed 12L/min, at the same with raw material pump with
The speed of 158g/min begins through the nozzle of injection reactor and spurts into MXDP solution, while opening reactor
Stirring, wherein the equivalent proportion of hydrogen chloride gas and phenylenedimethylidyne diamidogen amino is 1.5 in salt-forming reaction operation:1.Into salt
After end, the particle diameter of hydrochloric acid salt particle is determined using laser diffraction formula particle size analyzer in acetonitrile solution, and Jing determines hydrochloric acid salt particle
Number average bead diameter be 100um, phosgenation reaction kettle is warming up to into 145 DEG C then, is entered pipe with light air-blowing and light is blown into 53g/min
Gas, reaction absolute pressure are maintained at 0.5MPa, react 1.5h, and then reaction is carried out under absolute pressure 0.1Mpa, phosgene
It is 7.5g/min to be passed through speed, reacts 2h, after reaction terminates, by nitrogen is blown into into system, thus removes unreacted light
Gas and hydrogen chloride gas.The phosgenation liquid of gained is carried out into desolventizing, rectification obtains 1573g (yield is 93.0mol%) isophthalic
Dimethylene diisocyanate, product data refer to table 1.
1 properties of product test data table of table
Claims (14)
1. a kind of method for preparing isocyanates, comprises the steps：
(a) preliminary salt-forming reaction：Amine obtains amine hydrochlorate slurry Jing after inert organic solvents dilution with the preliminary salt-forming reaction of hydrogen chloride
Material；
B () is into salt slaking reaction：Amine hydrochlorate slurry obtained by step (a) is imported in reactor, while in adding there being polarity
Machine solvent, is passed through hydrogen chloride ripening salt-forming reaction, obtains ripening amine hydrochlorate slurry；
(c) pressurization phosgenation reaction：Ripening amine hydrochlorate slurry obtained by step (b) and phosgene are carried out into pressurization phosgenation reaction,
Obtain the reactant liquor containing isocyanates；
(d) product purification：Reactant liquor containing isocyanates obtained by step (c) is refining to obtain into isocyanate products；
Step (b) is described into the still reaction that salt slaking reaction device is the liquid slurry disperser that internal core part is hourglass shape
Device, the liquid slurry disperser of the hourglass shape is cylinder of the hourglass shape with bottom, hourglass shape cylinder upper and lower end face area phase
Deng or；
Step (b) the middle polar organic solvent is one or more in the ketone and nitrile of 50-100 DEG C of boiling point；In described
The consumption of polar organic solvent is the 5-20wt% of the amine hydrochlorate slurry gross mass obtained based on step (a)；
Step (a) inert organic solvents selected from benzene, toluene, chlorobenzene, o-dichlorohenzene, paracide, a chlordiphenyl, to benzene two
One or more in formic acid dialkyl ester and diethyl phthalate.
The cylinder of the liquid slurry disperser of hourglass shape described in step (b) is the porous tube for being arranged with star shape discharging opening
Body, the overall percent opening of the cylinder is 50-75%；
The star shape outer corners angle is less than or equal to 60 degree more than or equal to 15 degree；
The isocyanates have logical formula (I)：
R(NCO)n(I),
The amine has logical formula (II)：
R(NH2)n(II),
Wherein, n is 2；R represents m-phenylenedimethylim-, terephthalylidene.
2. the method for claim 1, is characterized in that, the liquid slurry disperser of the hourglass shape is on hourglass shape cylinder
The hourglass shape liquid slurry disperser of lower surface area equation.
3. the method for claim 1, is characterized in that, the height of the hourglass shape liquid slurry disperser is still reaction
The 1/4-1/2 of device height；The hourglass shape liquid slurry disperser lower surface is that autoclave is anti-with the distance of tank reactor bottom surface
Answer the 1/6-1/5 of device height；The stirring paddle of tank reactor is located at the liquid slurry disperser axle center of hourglass shape, stirrer paddle
Piece and the 1/4-1/3 that hourglass shape liquid slurry disperser lower surface distance is liquid slurry disperser height；The hourglass shape liquid
The 1/3-2/3 of a diameter of hourglass shape liquid slurry disperser lower surface circular diameter of the cross section smallest circle of body pulp stock disperser；Stir
Mix the 2/3-5/6 that paddle blade radical length is hourglass shape liquid slurry disperser lower surface circular diameter；Hourglass shape cylinder upper surface
The 3/4-5/4 of a diameter of lower surface diameter；The 2/5-3/5 of a diameter of reactor diameter in hourglass shape cylinder lower surface.
4. method as claimed in claim 3, is characterized in that, the height of the hourglass shape liquid slurry disperser is still reaction
The 1/3-1/2 of device height.
5. the method for claim 1, is characterized in that, based on whole cylinder height, the liquid slurry point of the hourglass shape
The cylinder upper surface of scattered device to the cylinder percent opening apart from upper surface 1/3 in be 55-70%, apart from upper surface 1/3 to away from
The percent opening of the cylinder between lower surface 1/3 is 50-60%, and cylinder lower surface is to the cylinder apart from lower surface 1/3 in
Percent opening is 60-75%.
6. the method for claim 1, is characterized in that, the star shape is triangle star, corner star, five-pointed star
One or more in shape, hexagram, heptangle star and anistree star.
7. the method as any one of claim 1-4, is characterized in that, step (b) the middle polar organic solvent is third
One or more in ketone, butanone and acetonitrile；The consumption of the middle polar organic solvent is the amine salt obtained based on step (a)
The 10-15wt% of hydrochlorate slurry gross mass.
8. the method for claim 1, is characterized in that, step (a) inert organic solvents are selected from o-dichlorohenzene.
9. the method as any one of claim 1-4, is characterized in that, the pressurization phosgenation reaction described in step (c) exists
Operate under the absolute pressure of 0.1-1.5MPa；Reaction temperature is 120-170 DEG C；Mean residence time is 1-600 minutes.
10. method as claimed in claim 9, is characterized in that, the pressurization phosgenation reaction described in step (c) is in 0.2-0.6MPa
Absolute pressure under operate；Reaction temperature is 140-150 DEG C；Mean residence time is 30-300 minutes.
11. methods as claimed in claim 10, is characterized in that, the mean residence time described in step (c) is 60-180 minutes.
12. the method for claim 1, is characterized in that, step (c) phosgene is in the form of pure phosgene or phosgene solution
It is passed through, the solvent of the phosgene solution is selected from benzene, toluene, chlorobenzene, o-dichlorohenzene, paracide, a chlordiphenyl, p-phthalic acid
One or more in dialkyl ester and diethyl phthalate；Phosgene in the phosgene solution accounts for the 10- of solvent quality
30wt%.
13. the method for claim 1, is characterized in that, the R represents m-phenylenedimethylim- or terephthalylidene.
14. methods as claimed in claim 13, is characterized in that, the R represents m-phenylenedimethylim-.
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| EP3444236B1 (en) * | 2016-04-11 | 2020-12-30 | Mitsui Chemicals, Inc. | Xylylenediisocyanate composition, resin, and polymerizable composition |
| CN108079921B (en) * | 2016-11-21 | 2020-08-28 | 万华化学集团股份有限公司 | Phosgenation reactor and method for preparing isocyanate by adopting same |
| CN107200691B (en) * | 2017-06-07 | 2020-04-14 | 江苏蓝丰生物化工股份有限公司 | Preparation method of substituted p-phenylenediamine hydrochloride |
| CN107597028B (en) * | 2017-09-21 | 2020-05-08 | 万华化学（宁波）有限公司 | Reactor and method for preparing isocyanate |
| CN107915662B (en) * | 2017-12-20 | 2020-10-02 | 青岛科技大学 | Device and method for separating and purifying m-xylylene diisocyanate |
| CN108640938A (en) * | 2018-04-26 | 2018-10-12 | 江西瑞合精细化工有限公司 | A kind of preparation method of high-melting-point boron chloride tertiary amines complex compound |
| CN111217975B (en) * | 2018-11-27 | 2022-01-07 | 万华化学集团股份有限公司 | Method for producing resin for optical material |
| CN109761855B (en) | 2018-12-20 | 2020-07-28 | 万华化学集团股份有限公司 | Method for preparing isophorone diisocyanate |
| CN110183356A (en) * | 2019-05-20 | 2019-08-30 | 江苏蓝丰生物化工股份有限公司 | Replace the application of the preparation method and non-nitrile polar organic solvent of class paraphenylene diisocyanate in its preparation |
| WO2021042251A1 (en) * | 2019-09-02 | 2021-03-11 | 万华化学集团股份有限公司 | Method for preparation of polyisocyanate by photochemical reaction and method for preparing waterborne polyurethane resin |
| CN112592457B (en) * | 2020-12-01 | 2023-04-07 | 万华化学集团股份有限公司 | Polyisocyanate composition and preparation method and application thereof |
| JP2023549053A (en) | 2020-12-01 | 2023-11-22 | 万華化学集団股▲フン▼有限公司 | Polyisocyanate compositions, methods of preparation and use thereof |
| CN112441951A (en) * | 2020-12-02 | 2021-03-05 | 甘肃银光聚银化工有限公司 | Method for synthesizing diisocyanate containing ether bond by salifying phosgenation method |
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| GB1086782A (en) * | 1965-02-19 | 1967-10-11 | Upjohn Co | Process for manufacturing polyisocyanates |
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| DE1593588C3 (en) * | 1965-09-06 | 1974-05-22 | Takeda Chemical Industries Ltd., Osaka (Japan) | Process for the preparation of m- and p-xylylene diisocyanate |
| CN102070491B (en) * | 2010-11-26 | 2013-12-18 | 万华化学集团股份有限公司 | Method for preparing xylylene diisocyanate based on salification-phosgenation reaction |
| CN104945283B (en) * | 2014-03-25 | 2016-10-19 | 万华化学集团股份有限公司 | A kind of method preparing isocyanate-monomer |
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