EP1799344A2 - Method for the continuous production of dmc catalysts - Google Patents
Method for the continuous production of dmc catalystsInfo
- Publication number
- EP1799344A2 EP1799344A2 EP05789181A EP05789181A EP1799344A2 EP 1799344 A2 EP1799344 A2 EP 1799344A2 EP 05789181 A EP05789181 A EP 05789181A EP 05789181 A EP05789181 A EP 05789181A EP 1799344 A2 EP1799344 A2 EP 1799344A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- dmc catalysts
- dmc
- catalysts
- reactor
- continuous
- 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.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims description 38
- 238000010924 continuous production Methods 0.000 title claims description 6
- 239000000725 suspension Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000013110 organic ligand Substances 0.000 claims abstract description 7
- -1 DMC compound Chemical class 0.000 claims abstract description 6
- 239000006259 organic additive Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims description 26
- 229920000570 polyether Polymers 0.000 claims description 25
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 23
- 150000001298 alcohols Chemical class 0.000 claims description 22
- 125000002947 alkylene group Chemical group 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- 238000011437 continuous method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 150000007942 carboxylates Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- RKBAPHPQTADBIK-UHFFFAOYSA-N cobalt;hexacyanide Chemical compound [Co].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] RKBAPHPQTADBIK-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 229920001983 poloxamer Polymers 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- HSINOMROUCMIEA-FGVHQWLLSA-N (2s,4r)-4-[(3r,5s,6r,7r,8s,9s,10s,13r,14s,17r)-6-ethyl-3,7-dihydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl]-2-methylpentanoic acid Chemical compound C([C@@]12C)C[C@@H](O)C[C@H]1[C@@H](CC)[C@@H](O)[C@@H]1[C@@H]2CC[C@]2(C)[C@@H]([C@H](C)C[C@H](C)C(O)=O)CC[C@H]21 HSINOMROUCMIEA-FGVHQWLLSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000003613 bile acid Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2663—Metal cyanide catalysts, i.e. DMC's
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/26—Cyanides
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/00033—Continuous processes
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00182—Controlling or regulating processes controlling the level of reactants in the reactor vessel
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
Definitions
- the invention relates to a process for the continuous preparation of multimetal cyanide compounds which can be used as catalysts for the addition of alkylene oxides to H-functional compounds. These compounds are often referred to as DMC compounds or DMC catalysts.
- DMC catalysts for the preparation of polyether alcohols by addition of alkylene oxides to H-functional compounds has long been known.
- the resulting polyether alcohols can be used as surface-active agents, as carrier oils, but mainly as starting materials for the preparation of polyurethanes.
- DMC catalysts lead to products with a lower content of unsaturated moieties in the polyether chain.
- the addition of the alkylene oxides takes place at a higher speed.
- the DMC catalysts are usually prepared by combining the solutions of a metal salt and a hexacyanometalate compound and subsequent separation, purification and, if appropriate, drying of the resulting polyimide cyanide compound. Usually, the production of the DMC catalysts takes place in the presence of ligands and / or surface-active agents.
- No. 5,891,818 discloses a process for the preparation of DMC catalysts by combining a metal salt solution with the solution of a hexacyanometallate compound, where part of the reaction mixture is taken off and returned to the reactor as a spray via a nozzle.
- the formation of foam in the reactor is suppressed and a better mixing of the reaction mixture can be effected.
- this procedure is still expensive and can lead to clogging of the nozzle by the catalyst particles.
- WO 01/39883 describes a process for the preparation of DMC catalysts in which a metal salt solution is mixed with the solution of a hexacyanometallate compound. tion is combined in a mixing nozzle.
- the disadvantage here is that it can already come in the nozzle to a particle formation, which leads to a pressure drop in the nozzle to blockages.
- the problem could be solved by continuously metering in a continuous reactor the educts used for the preparation of the DMC catalysts and continuously removing the resulting DMC catalyst from the reactor.
- the invention thus relates to a continuous process for the preparation of DMC catalysts, characterized in that the solutions of a metal salt and a HexacyanometallatENS and optionally organic ligands and / or organic additives are fed kontinuier ⁇ Lich in a continuous reactor and the resulting Suspension of the DMC compound is taken from the Re ⁇ actuator continuously.
- the invention furthermore relates to the DMC catalysts prepared by the process according to the invention and to their use for the preparation of polyether alcohols.
- tubular reactors and preferably continuous stirred tank reactors can be used.
- the resulting DMC catalyst suspension is continuously taken from the reactor. This can, in the case of using a continuous stirred tank as Reactor, for example, by a level control, coupled with a Boden ⁇ valve, a continuous withdrawal via a pump or an overflow be ensured tet.
- the average residence time in the reactor is preferably in the range between 1 and 180 minutes
- the temperature in the reactor is preferably between 10.. and 8O 0 C, particularly preferably between 15 and 60 0 C, in particular between 20 and 50 0 C.
- DMC catalysts with a high catalytic activity are obtained.
- a device for comminuting the particles formed can follow the course of the suspension from the reactor.
- a Nassro ⁇ tormühle be used. This leads to a more uniform distribution of the particle size in the suspension.
- the suspension of the DMC compound is usually supplied to a wash, filtration, redispersion and optionally drying. These work-up steps can also be operated continuously. However, it is also possible to collect the suspension in intermediate containers and to deliver them batchwise to the said work-up steps.
- the washing can be done either with water only, with an organic ligand or any mixtures of both.
- drying of the DMC catalysts is performed, this is done preferred wise at a temperature in the range between 20 and 150 0 C, in particular be- see 30 and 10O 0 C and a pressure between 0.01 bar and 1 bar, in particular Zvi ⁇ rule 0.05 bar and 0.7 bar.
- DMC catalysts prepared by the process according to the invention may have a different crystal structure, depending on the educts and auxiliaries used and the conditions of preparation.
- the DMC catalysts may have a crystalline or an amorphous structure.
- Crystalline DMC catalysts are described, for example, in WO 99/16775, amorphous DMC catalysts for example, described in EP 654 302.
- the catalysts may also be partially crystalline, that is, they contain both crystalline and amorphous portions.
- crystalline DMC catalysts those having a monoclinic crystal structure are particularly preferred.
- the DMC catalysts prepared by the process according to the invention have a platelet-like form, as described, for example, in WO 00/74845.
- the DMC catalysts prepared by the process according to the invention usually have the general formula (I)
- M 1 is a metal ion selected from the group consisting of Zn 2+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Ni 2+ , Mn 2+ , Sn 2+ , Sn 4+ , Pb 2+ , Mo 4+ , Mo 6+ , Al 3+ , V 4+ , V 5+ , Sr 2+ , W 4+ , W 6+ , Cr 2+ , Cr 3+ , Cd 2+ , Cu 2+ , La 3+ , Ce 3+ , Ce 4+ , Eu 3+ , Mg 2+ , Ti 3+ , Ti 4+ , Ag + , Rh 2+ , Ru 2+ , Ru 3+ , Pd 2+
- M 2 is a metal ion selected from the group consisting of Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Mn 2+ , Mn 3+ , Ni 2+ V 4+ , V 5+ , Cr 2+ , Cr 3+ , Rh 3+ , Ru 2+ , Ir 3+
- A is an anion selected from the group containing halide, hydroxide, sulfate, hydrogensulfate, carbonate, bicarbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate, nitrosyl, phosphate, hydrogen phosphate or dihydrogen phosphate
- X is an anion selected from the group comprising halide, hydroxide, sulfate, hydrogensulfate, carbonate, bicarbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate or nitrite (NO 2 " ) and the uncharged species CO , H 2 O and NO,
- L is a water-miscible ligand selected from the group comprising alcohols, aldehydes, ketones, ethers, polyethers, esters, polyesters, polycarbonate, ureas, amides, nitriles, and sulfides or mixtures thereof,
- P is an organic additive selected from the group comprising polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycides polyether, polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylamide-co-maleic acid), polyacrylonitrile, polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, Poly (N-vinylpyrrolidone-co-acrylic acid), polyvinyl methyl ketone, poly (4-vinylphenol), poly (acrylic acid-co-styrene), oxazoline polymers, polyalkyleneimines, maleic acid and maleic anhydride copolymer, hydroxyethylcellulose, polyacetates, ionic surfaces and surface-active compounds,
- a, b, d, q and n are integers or fractions greater than zero
- c, f, e, h and k are integers or fractions greater than or equal to zero
- a, b, c, and d, and q and n are selected so that the electroneutrality is ensured.
- these catalysts may be crystalline or amorphous.
- k is zero
- crystalline double metal cyanide compounds are preferred.
- k is greater than zero
- both crystalline, partially crystalline, and substantially amorphous catalysts are preferred.
- DMC catalysts of the general formula (I) prepared by the process according to the invention are those in which k is greater than zero.
- This DMC catalyst contains at least one multimetal cyanide compound, at least one organic ligand and at least one organic additive P.
- k is zero, optionally e is also zero, and X is exclusively carboxylate, preferably formate, acetate and propionate.
- crystalline double metal cyanide catalysts are preferred.
- M 1 are Zn 2+ , Fe 2+ , Co 2+ , Fe 3+ , Mn 2+ .
- Preferred examples of M 2 are Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Ir 3+ .
- Preferred examples of A are halide and carboxylate, especially acetate.
- At least one surfactant may be used in the preparation of the DMC catalysts.
- The- It is not incorporated into the catalyst and almost completely removed from the catalyst by washing the catalyst.
- the DMC catalysts prepared in this way have an improved morphology.
- organic sulfones of the general formula RS (O) 2 -R or sulfoxides of the general formula RS (O) -R are organic Complexing agent L used.
- the advantages of this embodiment are short induction times and moderate exotherm in the preparation of the polyether alcohols.
- the reaction is carried out at a pH of> 1, preferably> 4, more preferably> 7. These conditions produce crystalline DMC catalysts with a monoclinic crystal structure.
- f, e and k are equal to zero.
- DMC catalysts which contain a water-miscible organic ligand, preferably in amounts of from 0.5 to 30% by weight, and an organic additive, preferably in amounts of from 5 to 80% by weight.
- organic additive preferably in amounts of from 5 to 80% by weight.
- the catalysts can be used in a stirred tank with vigorous stirring, for example with a Turrax ®, prepared as described for example in US 5,158,922.
- the DMC compounds prepared by the process according to the invention were ⁇ most, as described, used as catalysts for the addition of alkylene oxides to H-functional starter substances.
- the products thus obtained can be used as surfactants, carrier oils or as polyether alcohols for the preparation of polyurethanes.
- alkylene oxides it is possible to use all known alkylene oxides, for example ethylene oxide, propylene oxide, butylene oxide, styrene oxide.
- alkoxide oxides used are ethylene oxide, propylene oxide and mixtures of the compounds mentioned.
- polyether alcohols for use as raw materials for polyurethane production are used as starting substances, in particular polyfunctional alcohols and as alkylene oxides, preferably ethylene oxide and / or propylene oxide.
- H-functional compounds are used.
- alcohols having a functionality of 1 to 8, preferably 2 to 8, are used.
- Alcohols having a functionality of 2 to 4, in particular 2 and 3, are preferably used as starting substances for the preparation of polyether alcohols which are employed for flexible polyurethane foams. Examples are ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol.
- alkylene oxides by means of DMC catalysts, it is advantageous to use together with or in place of the alcohols mentioned their reaction products with alkylene oxides, in particular propylene oxide.
- alkylene oxides in particular propylene oxide.
- Such compounds preferably have a molecular weight of up to 500 g / mol.
- the addition of the alkylene oxides in the preparation of these reaction products can be carried out with any catalysts, for example with basic catalysts.
- the polyether alcohols for the production of flexible polyurethane foams usually have a hydroxyl number in the range between 20 and 100 mg KOH / g.
- the addition of the alkylene oxides in the preparation of the polyether alcohols used for the process according to the invention can be carried out by the known processes.
- the polyether alcohols contain only one alkylene oxide.
- a so-called block-wise addition in which the alkylene oxides are added one after the other in succession, or a so-called statistical addition in which the alkylene oxides are added together is possible. It is also possible to incorporate both blockwise and random sections into the polyether chain in the preparation of the polyether alcohols.
- the mixture of starting substance and DMC catalyst can be pretreated by stripping prior to the beginning of the alkoxylation according to the teaching of WO 98/52689.
- the polyether alcohol is usually worked up by customary processes by removing the unreacted alkylene oxides and volatile constituents, usually by distillation, steam or gas stripping and or other methods of deodorization. If necessary, filtration can also be carried out.
- the catalyst can be separated off from the reaction mixture.
- the preparation of the polyether alcohols can also be carried out continuously. Such a procedure is described for example in WO 98/03571 or in JP H6-16806. In this process, alkylene oxides and starting substance are continuously metered into a continuous reactor and the resulting polyether alcohol is taken off continuously.
- polyether alcohols prepared using DMC catalysts are generally used for the production of flexible polyurethane foams by reaction with polyisocyanates.
- the DMC catalysts prepared by the process according to the invention have no disadvantages in their properties over other catalysts prepared by the conventional batch process.
- the expense in the production of the DMC catalysts can be significantly reduced.
- the DMC catalysts prepared by the process according to the invention have the same properties.
- Solution 1 consisted of an aqueous zinc acetate solution (2.6% zinc), Solution 2 of an aqueous solution of potassium hexacyanocobaltate with 0.9% cobalt.
- Solution 1 at 7.91 kg / h and solution 2 at 10 kg / h were metered through a mixing nozzle into a 3 liter stirred tank. Both solutions contained 2 wt .-% of a surfactant (Pluronic PE6200 ® of BASF AG). After filling the stirred tank, the feed was stopped and the present DMC suspension stirred at a temperature of 20 0 C in the stirred tank and an energy input by stirring 1 W / l for 1 h. Subsequently, the catalyst was filtered off, washed with water and dried at 6O 0 C.
- a surfactant Pluronic PE6200 ® of BASF AG
- Solution 1 consisted of an aqueous zinc acetate solution (2.6% zinc), Solution 2 of an aqueous solution of potassium hexacyanocobaltate with 0.9% cobalt.
- Solution 1 at 7.91 kg / h and solution 2 at 10 kg / h were metered continuously through a mixing nozzle into a 3 liter stirred tank. Both solutions contained 2 wt .-% of a surface-active agent (Pluronic ® PE6200 BASF AG).
- the present DMC suspension was at a temperature of 20 0 C in a stirred tank and an energy input by stirring 1 W / l glallstandsge- regulates via a bottom drain valve continuously drained. The average residence time in the stirred tank was 10 min. To ensure the steady state, the experiment was carried out over 10 mean residence times. Subsequently, the catalyst was filtered off, washed with water and dried at 6O 0 C.
- Solution 1 consisted of an aqueous zinc acetate solution (2.6% zinc), Solution 2 of an aqueous solution of potassium hexacyanocobaltate with 0.9% cobalt.
- Solution 1 at 3.95 kg / h and solution 2 at 5 kg / h were metered continuously via inlet tubes into a 3 liter stirred vessel. Both solutions contained 2 wt .-% of a devis perenniali ⁇ ven agent (Pluronic ® PE6200 BASF AG).
- the present DMC suspension was continuously discharged at a temperature of 35 ° C in a stirred tank and an energy input by stirring of 1 W / l Medstandsge ⁇ regulated via a bottom drain valve. The average residence time in the stirred tank was 20 min. To ensure the steady state, the experiment was carried out over 10 mean residence times. Subsequently, the catalyst was filtered off, washed with water and dried at 60 0 C.
- Example 1 100 8 8,6bar / 165 ° C
- Example 2 100 7 8,9bar / 175 ° C
- Example 3 100 10 8,4bar / 169 ° C
- the catalytic activity of the DMC catalysts prepared by the process according to the invention is comparable to that of conventional DMC catalysts.
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Abstract
The invention relates to a continuous method for producing DMC catalysts, which is characterized in that the solutions of a metal salt and a hexacyanometallate compound and optionally organic ligands and/or organic additives are continuously fed to a continuous reactor and the suspension of the DMC compound formed is continuously removed from the reactor.
Description
Verfahren zur kontinuierlichen Herstellung von DMC-KatalysatorenProcess for the continuous production of DMC catalysts
Gegenstand der Erfindung ist ein Verfahren zur kontinuierlichen Herstellung von Multi- metallcyanidverbindungen, die als Katalysatoren für die Anlagerung von Alkylenoxiden an H-funktionelle Verbindungen eingesetzt werden können. Diese Verbindungen wer¬ den häufig auch als DMC-Verbindungen oder DMC-Katalysatoren bezeichnet.The invention relates to a process for the continuous preparation of multimetal cyanide compounds which can be used as catalysts for the addition of alkylene oxides to H-functional compounds. These compounds are often referred to as DMC compounds or DMC catalysts.
Der Einsatz von DMC-Katalysatoren zur Herstellung von Polyetheralkoholen durch Anlagerung von Alkylenoxiden an H-funktionelle Verbindungen ist seit langem bekannt. Die resultierenden Polyetheralkohole können als oberflächenaktive Mittel, als Träger¬ öle, hauptsächlich jedoch als Ausgangsprodukte zur Herstellung von Polyurethanen eingesetzt werden. Gegenüber basischen Katalysatoren führen DMC-Katalysatoren zu Produkten mit einem geringeren Gehalt an ungesättigten Anteilen in der Polyetherket- te. Außerdem erfolgt die Anlagerung der Alkylenoxide mit einer höheren Geschwindig- keit.The use of DMC catalysts for the preparation of polyether alcohols by addition of alkylene oxides to H-functional compounds has long been known. The resulting polyether alcohols can be used as surface-active agents, as carrier oils, but mainly as starting materials for the preparation of polyurethanes. Compared to basic catalysts, DMC catalysts lead to products with a lower content of unsaturated moieties in the polyether chain. In addition, the addition of the alkylene oxides takes place at a higher speed.
Es ist eine Vielzahl von Dokumenten zu DMC-Katalysatoren, deren Herstellung, Kris¬ tallstruktur sowie Anwendung zur Herstellung von Polyurethanen bekannt.There is a large number of documents on DMC catalysts, their preparation, Kris¬ tallstruktur and application for the production of polyurethanes known.
Die Herstellung der DMC-Katalysatoren erfolgt üblicherweise durch Vereinigung der Lösungen eines Metallsalzes und einer Hexacyanometallatverbindung und nachfol¬ gender Abtrennung, Reinigung und gegebenenfalls Trocknung der entstehenden MuI- timetallcyanidverbindung. Üblicherweise erfolgt die Herstellung der DMC-Katalysatoren in Anwesenheit von Liganden und/oder oberflächenaktiven Mitteln.The DMC catalysts are usually prepared by combining the solutions of a metal salt and a hexacyanometalate compound and subsequent separation, purification and, if appropriate, drying of the resulting polyimide cyanide compound. Usually, the production of the DMC catalysts takes place in the presence of ligands and / or surface-active agents.
Derartige Verfahren sind beispielsweise in US 3,278,458, EP 862 997 und DD 203 734 beschrieben.Such methods are described for example in US 3,278,458, EP 862 997 and DD 203 734.
Da die Herstellung der DMC-Katalysatoren aufwendig ist, hat es in der Vergangenheit nicht an Versuchen gefehlt, die Herstellung zu vereinfachen. So beschreibtSince the preparation of the DMC catalysts is complicated, there has been no lack of attempts in the past to simplify the production. So describes
US 5,891 ,818 ein Verfahren zur Herstellung von DMC-Katalysatoren durch Vereini¬ gung einer Metallsalzlösung mit der Lösung einer Hexacyanometallatverbindung, wo¬ bei ein Teil der Reaktionsmischung abgenommen und über eine Düse als Spray in den Reaktor zurückgeführt wird. Durch diese Verfahrensweise soll die Schaumbildung im Reaktor unterdrückt und eine bessere Durchmischung der Reaktionsmischung bewirkt werden. Im Kreislauf befindet sich ein in-line-Mischer, durch den auf Grund der Scher¬ kräfte die Katalysatorpartikel weiter zerkleinert werden, was zu einer höheren Aktivität des Katalysators führt. Diese Verfahrensweise ist jedoch immer noch aufwendig, und es kann zu einer Verstopfung der Düse durch die Katalysatorpartikel kommen.No. 5,891,818 discloses a process for the preparation of DMC catalysts by combining a metal salt solution with the solution of a hexacyanometallate compound, where part of the reaction mixture is taken off and returned to the reactor as a spray via a nozzle. By this procedure, the formation of foam in the reactor is suppressed and a better mixing of the reaction mixture can be effected. There is an in-line mixer in the circuit through which the catalyst particles are further comminuted due to the shear forces, which leads to a higher activity of the catalyst. However, this procedure is still expensive and can lead to clogging of the nozzle by the catalyst particles.
In WO 01/39883 wird ein Verfahren zur Herstellung von DMC-Katalysatoren beschrie¬ ben, bei dem eine Metallsalzlösung mit der Lösung einer Hexacyanometallatverbin-
dung in einer Mischdüse vereinigt wird. Nachteilig ist hierbei, dass es bereits in der Düse zu einer Partikelbildung kommen kann, was zu einem Druckverlust in der Düse bis hin zu Verstopfungen führt.WO 01/39883 describes a process for the preparation of DMC catalysts in which a metal salt solution is mixed with the solution of a hexacyanometallate compound. tion is combined in a mixing nozzle. The disadvantage here is that it can already come in the nozzle to a particle formation, which leads to a pressure drop in the nozzle to blockages.
Nachteilig an allen Batchverfahren zur Herstellung von DMC-Katalysatoren ist weiter¬ hin, dass die Produktparameter der einzelnen Chargen unterschiedlich sein können.Another disadvantage of all batch processes for the preparation of DMC catalysts is that the product parameters of the individual batches can be different.
Aufgabe der Erfindung war es, ein Verfahren zur Herstellung von DMC-Katalysatoren zu entwickeln, bei dem auf einfache und betriebssichere Weise, mit gleichbleibender Qualität und hoher Raum-Zeit-Ausbeute DMC-Katalysatoren hergestellt werden kön¬ nen. Dabei sollte es zu keiner Verschlechterung der katalytischen Aktivität der DMC- Katalysatoren kommen.It was an object of the invention to develop a process for the preparation of DMC catalysts in which DMC catalysts can be prepared in a simple and reliable manner with constant quality and high space-time yield. There should be no deterioration in the catalytic activity of the DMC catalysts.
Die Aufgabe konnte überraschenderweise gelöst werden, indem in einen kontinuierli- chen Reaktor kontinuierlich die zur Herstellung der DMC-Katalysatoren eingesetzten Edukte eindosiert werden und der erhaltene DMC-Katalysator dem Reaktor kontinuier¬ lich entnommen wird.Surprisingly, the problem could be solved by continuously metering in a continuous reactor the educts used for the preparation of the DMC catalysts and continuously removing the resulting DMC catalyst from the reactor.
Gegenstand der Erfindung ist somit ein kontinuierliches Verfahren zur Herstellung von DMC-Katalysatoren, dadurch gekennzeichnet, dass in einen kontinuierlich arbeitenden Reaktor die Lösungen eines Metallsalzes und einer Hexacyanometallatverbindung so¬ wie gegebenenfalls organische Liganden und/oder organische Zusatzstoffe kontinuier¬ lich zugeführt werden und die entstehende Suspension der DMC-Verbindung dem Re¬ aktor kontinuierlich entnommen wird.The invention thus relates to a continuous process for the preparation of DMC catalysts, characterized in that the solutions of a metal salt and a Hexacyanometallatverbindung and optionally organic ligands and / or organic additives are fed kontinuier¬ Lich in a continuous reactor and the resulting Suspension of the DMC compound is taken from the Re¬ actuator continuously.
Gegenstand der Erfindung sind weiterhin die nach dem erfindungsgemäßen Verfahren hergestellten DMC-Katalysatoren sowie deren Verwendung zur Herstellung von PoIy- etheralkoholen.The invention furthermore relates to the DMC catalysts prepared by the process according to the invention and to their use for the preparation of polyether alcohols.
Als kontinuierlich arbeitende Reaktoren können Rohrreaktoren und vorzugsweise kon¬ tinuierliche Rührkesselreaktoren eingesetzt werden.As continuously operating reactors tubular reactors and preferably continuous stirred tank reactors can be used.
Die Zugabe der Lösungen des Metallsalzes und der Hexacyanometallatverbindung, im folgenden auch als Eduktlösungen bezeichnet, in den Reaktor, insbesondere den kon- tinuierlich arbeitenden Rührkessel, kann durch eine Mischdüse oder durch Einleitrohre auf die Oberfläche der Reaktionsmischung oder getaucht erfolgen. Der Einsatz von Mischdüsen zur Vorvermischung der Eduktlösungen ist dabei nicht notwendig. Damit entfällt das Risiko einer Verstopfung der Düsen, was zu einer gleichmäßigen und stö¬ rungsfreien Arbeitsweise des Reaktors führt.The addition of the solutions of the metal salt and the Hexacyanometallatverbindung, hereinafter also referred to as Eduktlösungen in the reactor, in particular the continuous stirred tank, can be done by a mixing nozzle or through inlet pipes on the surface of the reaction mixture or immersed. The use of mixing nozzles for premixing the educt solutions is not necessary. This eliminates the risk of clogging of the nozzles, which leads to a uniform and trouble-free operation of the reactor.
Die entstehende DMC-Katalysatorsuspension wird kontinuierlich aus dem Reaktor ent¬ nommen. Dies kann, im Falle der Verwendung eines kontinuierlichen Rührkessels als
Reaktor, beispielsweise durch eine Füllstandsregelung, gekoppelt mit einem Boden¬ ventil, einem kontinuierlichen Abzug über eine Pumpe oder einem Überlauf gewährleis¬ tet werden.The resulting DMC catalyst suspension is continuously taken from the reactor. This can, in the case of using a continuous stirred tank as Reactor, for example, by a level control, coupled with a Boden¬ valve, a continuous withdrawal via a pump or an overflow be ensured tet.
Bei der Verwendung eines kontinuierlich arbeitenden Rührkessels erfolgt vorzugsweise ein Energieeintrag durch den Rührer im Bereich zwischen 10"2- 10 kW/m3. Die mittlere Verweilzeit im Reaktor liegt vorzugsweise im Bereich zwischen 1 und 180 Minuten. Die Temperatur im Reaktor liegt vorzugsweise zwischen 10 und 8O0C, besonders bevor¬ zugt zwischen 15 und 6O0C, insbesondere zwischen 20 und 500C.When using a continuous stirred tank preferably an energy input by the stirrer in the range between 10 "2 to 10 kW / m 3, the average residence time in the reactor is preferably in the range between 1 and 180 minutes, the temperature in the reactor is preferably between 10.. and 8O 0 C, particularly preferably between 15 and 60 0 C, in particular between 20 and 50 0 C.
Bei Einhaltung dieser Bedingungen werden DMC-Katalysatoren mit einer hohen kataly- tischen Aktivität erhalten.When these conditions are met, DMC catalysts with a high catalytic activity are obtained.
An den Ablauf der Suspension aus dem Reaktor kann sich eine Vorrichtung zum Zer- kleinern der gebildeten Partikel anschließen. Hierzu kann beispielsweise eine Nassro¬ tormühle eingesetzt werden. Dies führt zu einer gleichmäßigeren Verteilung der Parti¬ kelgröße in der Suspension.A device for comminuting the particles formed can follow the course of the suspension from the reactor. For this purpose, for example, a Nassro¬ tormühle be used. This leads to a more uniform distribution of the particle size in the suspension.
Nach der Entnahme aus dem Reaktor wird die Suspension der DMC-Verbindung übli- cherweise einer Waschung, Filtration, Redispergierung und gegebenenfalls einer Trocknung zugeführt. Diese Aufarbeitungsschritte können ebenfalls kontinuierlich be¬ trieben werden. Es ist jedoch auch möglich, die Suspension in Zwischenbehältern zu sammeln und diskontinuierlich den genannten Aufarbeitungsschritten zuzuführen.After removal from the reactor, the suspension of the DMC compound is usually supplied to a wash, filtration, redispersion and optionally drying. These work-up steps can also be operated continuously. However, it is also possible to collect the suspension in intermediate containers and to deliver them batchwise to the said work-up steps.
Die Waschung kann entweder nur mit Wasser, mit einem organischen Liganden oder beliebigen Gemischen aus beiden erfolgen.The washing can be done either with water only, with an organic ligand or any mixtures of both.
Es ist prinzipiell auch möglich, auf die Trocknung der DMC-Katalysatoren zu verzichten und sie in der redispergierten Form als Suspension zur Herstellung der Polyetheralko- hole einzusetzen. Es ist ebenso möglich, den D MC-Katalysator nach der Trocknung zu suspendieren und in dieser Form zur Herstellung der Polyetheralkohole einzusetzen.It is also possible in principle to dispense with the drying of the DMC catalysts and to use them in the redispersed form as a suspension for the preparation of the polyether alcohols. It is also possible to suspend the D MC catalyst after drying and to use it in this form for the preparation of the polyether alcohols.
Falls eine Trocknung der DMC-Katalysatoren durchgeführt wird, erfolgt diese vorzugs¬ weise bei einer Temperatur im Bereich zwischen 20 und 1500C, insbesondere zwi- sehen 30 und 10O0C und einem Druck zwischen 0,01 bar und 1 bar, insbesondere zwi¬ schen 0,05 bar und 0,7 bar.If drying of the DMC catalysts is performed, this is done preferred wise at a temperature in the range between 20 and 150 0 C, in particular be- see 30 and 10O 0 C and a pressure between 0.01 bar and 1 bar, in particular Zvi ¬ rule 0.05 bar and 0.7 bar.
Nach dem erfindungsgemäßen Verfahren hergestellte DMC-Katalysatoren können, je nach den eingesetzten Edukten sowie Hilfsstoffen und den Herstellungsbedingungen eine unterschiedliche Kristallstruktur aufweisen. So können die DMC-Katalysatoren einen kristallinen oder einen amorphen Aufbau besitzen. Kristalline DMC-Katalysatoren sind beispielsweise beschrieben in WO 99/16775, amorphe DMC-Katalysatoren sind
beispielsweise beschrieben in EP 654 302. Die Katalysatoren können auch teilkristallin sein, das heißt, dass sie sowohl kristalline als auch amorphe Anteile enthalten.DMC catalysts prepared by the process according to the invention may have a different crystal structure, depending on the educts and auxiliaries used and the conditions of preparation. Thus, the DMC catalysts may have a crystalline or an amorphous structure. Crystalline DMC catalysts are described, for example, in WO 99/16775, amorphous DMC catalysts for example, described in EP 654 302. The catalysts may also be partially crystalline, that is, they contain both crystalline and amorphous portions.
Unter den kristallinen DMC-Katalysatoren sind solche mit einer monoklinen Kristall- struktur besonders bevorzugt.Among the crystalline DMC catalysts, those having a monoclinic crystal structure are particularly preferred.
In einer weiteren bevorzugten Ausführungsform weisen die nach dem erfindungsge¬ mäßen Verfahren hergestellten DMC-Katalysatoren eine plättchenförmige Gestalt auf, wie beispielsweise in WO 00/74845 beschrieben.In a further preferred embodiment, the DMC catalysts prepared by the process according to the invention have a platelet-like form, as described, for example, in WO 00/74845.
Die nach dem erfindungsgemäßen Verfahren hergestellten DMC-Katalysatoren haben zumeist die allgemeine Formel (I)The DMC catalysts prepared by the process according to the invention usually have the general formula (I)
M1a[M2(CN)b(A)c]d-fM1 gXn-h(H20) eL-kP (I)M 1 a [M 2 (CN) b (A) c ] d -fM 1 g X n -h (H 2 O) eL-kP (I)
wobeiin which
M1 ein Metallion, ausgewählt aus der Gruppe, enthaltend Zn2+, Fe2+, Fe3+, Co2+, Co3+, Ni2+, Mn2+, Sn2+, Sn4+, Pb2+, Mo4+, Mo6+, Al3+, V4+, V5+, Sr2+, W4+, W6+, Cr2+, Cr3+, Cd2+, Cu2+, La3+, Ce3+, Ce4+, Eu3+, Mg2+, Ti3+, Ti4+, Ag+, Rh2+, Ru2+, Ru3+, Pd2+ M 1 is a metal ion selected from the group consisting of Zn 2+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Ni 2+ , Mn 2+ , Sn 2+ , Sn 4+ , Pb 2+ , Mo 4+ , Mo 6+ , Al 3+ , V 4+ , V 5+ , Sr 2+ , W 4+ , W 6+ , Cr 2+ , Cr 3+ , Cd 2+ , Cu 2+ , La 3+ , Ce 3+ , Ce 4+ , Eu 3+ , Mg 2+ , Ti 3+ , Ti 4+ , Ag + , Rh 2+ , Ru 2+ , Ru 3+ , Pd 2+
M2 ein Metallion, ausgewählt aus der Gruppe, enthaltend Fe2+, Fe3+, Co2+, Co3+, Mn2+, Mn3+, Ni2+ V4+, V5+, Cr2+, Cr3+, Rh3+, Ru2+, Ir3+ M 2 is a metal ion selected from the group consisting of Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Mn 2+ , Mn 3+ , Ni 2+ V 4+ , V 5+ , Cr 2+ , Cr 3+ , Rh 3+ , Ru 2+ , Ir 3+
bedeuten und M1 und M2 verschieden sind,mean and M 1 and M 2 are different,
A ein Anion, ausgewählt aus der Gruppe, enthaltend Halogenid, Hydroxyd, Sulfat, Hydrogensulfat, Carbonat, Hydrogencarbonat, Cyanid, Thiocyanat, Isocyanat, Cyanat, Carboxylat, Oxalat, Nitrat, Nitrosyl, Phosphat, Hydrogenphosphat oder DihydrogenphosphatA is an anion selected from the group containing halide, hydroxide, sulfate, hydrogensulfate, carbonate, bicarbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate, nitrosyl, phosphate, hydrogen phosphate or dihydrogen phosphate
X ein Anion, ausgewählt aus der Gruppe, enthaltend Halogenid, Hydroxyd, Sulfat, Hydrogensulfat, Carbonat, Hydrogencarbonat, Cyanid, Thiocyanat, Isocyanat, Cyanat, Carboxylat, Oxalat, Nitrat oder Nitrit (NO2 "). sowie die ungeladene Spe- zies CO, H2O und NO,X is an anion selected from the group comprising halide, hydroxide, sulfate, hydrogensulfate, carbonate, bicarbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate or nitrite (NO 2 " ) and the uncharged species CO , H 2 O and NO,
L ein mit Wasser mischbarer Ligand, ausgewählt aus der Gruppe, enthaltend Al¬ kohole Aldehyde, Ketone, Ether, Polyether, Ester, Polyester, Polycarbonat, Harnstoffe, Amide, Nitrile, und Sulfide oder deren Mischungen,L is a water-miscible ligand selected from the group comprising alcohols, aldehydes, ketones, ethers, polyethers, esters, polyesters, polycarbonate, ureas, amides, nitriles, and sulfides or mixtures thereof,
P ein organischer Zusatzstoff, ausgewählt aus der Gruppe, enthaltend Polyether, Polyester, Polycarbonate, Polyalkylenglykolsorbitanester, Polyalkylenglykolglyci-
dylether, Polyacrylamid, Poly(acrylamid-co-acrylsäure), Polyacrylsäure, Po- ly(acrylamid-co-maleinsäure), Polyacrylnitril, Polyalkylacrylate, Polyalkylmethac- rylate, Polyvinylmethylether, Polyvinylethylether, Polyvinylacetat, Polyvinylalko- hol, Poly-N-vinylpyrrolidon, Poly(N-vinylpyrrolidon-co-acrylsäure), Polyvinylme- thylketon, Poly(4-vinylphenol), Poly(acrylsäure-co-styrol), Oxazolinpolymere, Po- lyalkylenimine, Maleinsäure und Maleinsäureanhydridcopolymer, Hydroxyethyl- cellulose, Polyacetate, ionische Oberflächen und grenzflächenaktive Verbindun¬ gen, Gallensäure oder deren Salze, Ester oder Amide, Carbonsäureester mehr¬ wertiger Alkohole und Glycoside.P is an organic additive selected from the group comprising polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycides polyether, polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylamide-co-maleic acid), polyacrylonitrile, polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, Poly (N-vinylpyrrolidone-co-acrylic acid), polyvinyl methyl ketone, poly (4-vinylphenol), poly (acrylic acid-co-styrene), oxazoline polymers, polyalkyleneimines, maleic acid and maleic anhydride copolymer, hydroxyethylcellulose, polyacetates, ionic surfaces and surface-active compounds, bile acid or its salts, esters or amides, carboxylic esters of polyhydric alcohols and glycosides.
sowiesuch as
a, b, d, q und n ganze oder gebrochene Zahlen größer null, c, f, e, h und k ganze oder gebrochene Zahlen größer gleich null sind,a, b, d, q and n are integers or fractions greater than zero, c, f, e, h and k are integers or fractions greater than or equal to zero,
wobeiin which
a, b, c,und d, sowie q und n so ausgewählt sind, dass die Elektroneutralität gewährleis¬ tet ist.a, b, c, and d, and q and n are selected so that the electroneutrality is ensured.
Diese Katalysatoren können, wie beschrieben, kristallin oder amorph sein. Für den Fall, dass k gleich null ist, sind kristalline Doppelmetallcyanidverbindungen bevorzugt. Im Fall, dass k größer null ist, sind sowohl kristalline, teilkristalline, als auch substantiell amorphe Katalysatoren bevorzugt.As described, these catalysts may be crystalline or amorphous. In the case where k is zero, crystalline double metal cyanide compounds are preferred. In the case where k is greater than zero, both crystalline, partially crystalline, and substantially amorphous catalysts are preferred.
Eine bevorzugte Ausführungsform der nach dem erfindungsgemäßen Verfahren her¬ gestellten DMC-Katalysatoren der allgemeinen Formel (I) sind solche, bei denen k grö¬ ßer null ist. Dieser DMC-Katalysator enthält mindestens eine Multimetallcyanidverbin- dung, mindestens einen organischen Liganden und mindestens einen organischen Zusatzstoff P.A preferred embodiment of the DMC catalysts of the general formula (I) prepared by the process according to the invention are those in which k is greater than zero. This DMC catalyst contains at least one multimetal cyanide compound, at least one organic ligand and at least one organic additive P.
Bei einer anderen bevorzugten Ausführungsform ist k gleich null, optional e auch gleich null und X ist ausschließlich Carboxylat, bevorzugt Formiat, Acetat und Propionat. Bei dieser Ausführungsform, die beispielsweise in WO 99/16775 beschrieben ist, sind kri- stalline Doppelmetallcyanid-Katalysatoren bevorzugt.In another preferred embodiment, k is zero, optionally e is also zero, and X is exclusively carboxylate, preferably formate, acetate and propionate. In this embodiment, which is described, for example, in WO 99/16775, crystalline double metal cyanide catalysts are preferred.
Bevorzugte Beispiele für M1 sind Zn2+, Fe2+, Co2+, Fe3+, Mn2+. Bevorzugte Beispiele für M2 sind Fe2+, Fe3+, Co2+, Co3+, Ir3+. Bevorzugte Beispiele für A sind Halogenid und Carboxylat, insbesondere Acetat.Preferred examples of M 1 are Zn 2+ , Fe 2+ , Co 2+ , Fe 3+ , Mn 2+ . Preferred examples of M 2 are Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Ir 3+ . Preferred examples of A are halide and carboxylate, especially acetate.
Gemeinsam mit oder an Stelle von organischen Liganden kann bei der Herstellung der DMC-Katalysatoren mindestens ein oberflächenaktives Mittel eingesetzt werden. Die-
ses wird nicht in den Katalysator eingebaut und durch das Waschen des Katalysators praktisch vollständig aus dem Katalysator entfernt. Die so hergestellten DMC-Kataly- satoren weisen eine verbesserte Morphologie auf.Together with or instead of organic ligands, at least one surfactant may be used in the preparation of the DMC catalysts. The- It is not incorporated into the catalyst and almost completely removed from the catalyst by washing the catalyst. The DMC catalysts prepared in this way have an improved morphology.
In einer weiteren Ausführungsform der nach dem erfindungsgemäßen Verfahren her¬ gestellten DMC-Katalysatoren werden, wie in WO 01/03830 beschrieben, organische Sulfone der allgemeinen Form R-S(O)2-R oder Sulfoxide der allgemeinen Form R-S(O)-R als organisches komplexierendes Agens L eingesetzt. Die Vorteile dieser Ausführungsform sind kurze Induktionszeiten und moderate Exothermie bei der Her- Stellung der Polyetheralkohole.In a further embodiment of the DMC catalysts prepared by the process according to the invention, as described in WO 01/03830, organic sulfones of the general formula RS (O) 2 -R or sulfoxides of the general formula RS (O) -R are organic Complexing agent L used. The advantages of this embodiment are short induction times and moderate exotherm in the preparation of the polyether alcohols.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird die Umsetzung bei einem pH-Wert >1 , bevorzugt >4, besonders bevorzugt >7 durchge¬ führt. Bei diesen Bedingungen entstehen kristalline DMC-Katalysatoren mit einer mo- noklinen Kristallstruktur.In a preferred embodiment of the process according to the invention, the reaction is carried out at a pH of> 1, preferably> 4, more preferably> 7. These conditions produce crystalline DMC catalysts with a monoclinic crystal structure.
Bei einer anderen bevorzugten Ausführungsform der Katalysatoren sind f, e und k un¬ gleich Null. Dabei handelt es sich um DMC-Katalysatoren, die einen mit Wasser mischbaren organischen Liganden, vorzugsweise in Mengen von 0,5 bis 30 Gew.-%, und einen organischen Zusatzstoff, vorzugsweise in Mengen von 5 bis 80 Gew.-%, enthalten. Derartige Katalysatoren sind beispielsweise in WO 98/06312 beschrieben.In another preferred embodiment of the catalysts, f, e and k are equal to zero. These are DMC catalysts which contain a water-miscible organic ligand, preferably in amounts of from 0.5 to 30% by weight, and an organic additive, preferably in amounts of from 5 to 80% by weight. Such catalysts are described, for example, in WO 98/06312.
Die Katalysatoren können bei Verwendung eines Rührkessels unter starkem Rühren, beispielsweise mit einem Turrax®, hergestellt werden, wie beispielsweise in US 5,158,922 beschrieben., The catalysts can be used in a stirred tank with vigorous stirring, for example with a Turrax ®, prepared as described for example in US 5,158,922.
Die nach dem erfindungsgemäßen Verfahren hergestellten DMC-Verbindungen wer¬ den zumeist, wie beschrieben, als Katalysatoren zur Anlagerung von Alkylenoxiden an H-funktionelle Startsubstanzen eingesetzt. Die so erhaltenen Produkte können als oberflächenaktive Mittel, Trägeröle oder als Polyetheralkohole für die Herstellung von Polyurethanen eingesetzt werden.The DMC compounds prepared by the process according to the invention wer¬ most, as described, used as catalysts for the addition of alkylene oxides to H-functional starter substances. The products thus obtained can be used as surfactants, carrier oils or as polyether alcohols for the preparation of polyurethanes.
Als Alkylenoxide können alle bekannten Alkylenoxide verwendet werden, beispielswei¬ se Ethylenoxid, Propylenoxid, Butylenoxid, Styroloxid. Insbesondere werden als Alky- tenoxide Ethylenoxid, Propylenoxid und Mischungen aus den genannten Verbindungen eingesetzt.As alkylene oxides, it is possible to use all known alkylene oxides, for example ethylene oxide, propylene oxide, butylene oxide, styrene oxide. In particular, the alkoxide oxides used are ethylene oxide, propylene oxide and mixtures of the compounds mentioned.
Zur Herstellung von Polyetheralkoholen für den Einsatz als Rohstoffe zur Polyurethan- Herstellung kommen als Startsubstanzen insbesondere mehrfunktionelle Alkohole und als Alkylenoxide vorzugsweise Ethylenoxid und/oder Propylenoxid zum Einsatz.
Als Startsubstanzen kommen H-funktionelle Verbindungen zum Einsatz. Insbesondere werden Alkohole mit einer Funktionalität von 1 bis 8, vorzugsweise 2 bis 8, eingesetzt. Zur Herstellung von Polyetheralkoholen, die für Polyurethan-Weichschaumstoffe ein¬ gesetzt werden, kommen als Startsubstanzen vorzugsweise Alkohole mit einer Funkti- onalität von 2 bis 4, insbesondere von 2 und 3, zum Einsatz. Beispiele sind Ethylengly- kol, Propylenglykol, Glyzerin, Trimethylolpropan, Pentaerythrit. Bei der Anlagerung der Alkylenoxide mittels DMC-Katalysatoren ist es vorteilhaft, zusammen mit oder an Stelle von den genannten Alkoholen deren Umsetzungsprodukte mit Alkylenoxiden, insbe¬ sondere Propylenoxid, einzusetzen. Derartige Verbindungen haben vorzugsweise eine Molmasse bis 500 g/mol. Die Anlagerung der Alkylenoxide bei der Herstellung dieser Umsetzungsprodukte kann mit beliebigen Katalysatoren erfolgen, beispielsweise mit basischen Katalysatoren. Die Polyetheralkohole für die Herstellung von Polyurethan- Weichschaumstoffen haben zumeist eine Hydroxylzahl im Bereich zwischen 20 und 100 mg KOH/g.For the preparation of polyether alcohols for use as raw materials for polyurethane production are used as starting substances, in particular polyfunctional alcohols and as alkylene oxides, preferably ethylene oxide and / or propylene oxide. As starting substances H-functional compounds are used. In particular, alcohols having a functionality of 1 to 8, preferably 2 to 8, are used. Alcohols having a functionality of 2 to 4, in particular 2 and 3, are preferably used as starting substances for the preparation of polyether alcohols which are employed for flexible polyurethane foams. Examples are ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol. In the addition of the alkylene oxides by means of DMC catalysts, it is advantageous to use together with or in place of the alcohols mentioned their reaction products with alkylene oxides, in particular propylene oxide. Such compounds preferably have a molecular weight of up to 500 g / mol. The addition of the alkylene oxides in the preparation of these reaction products can be carried out with any catalysts, for example with basic catalysts. The polyether alcohols for the production of flexible polyurethane foams usually have a hydroxyl number in the range between 20 and 100 mg KOH / g.
Die Anlagerung der Alkylenoxide bei der Herstellung der für das erfindungsgemäße Verfahren eingesetzten Polyetheralkohole kann nach den bekannten Verfahren erfol¬ gen. So ist es möglich, dass die Polyetheralkohole nur ein Alkylenoxid enthalten. Bei Verwendung von mehreren Alkylenoxiden ist eine sogenannte blockweise Anlagerung, bei der die Alkylenoxide einzeln nacheinander angelagert werden, oder eine sogenann¬ te statistische Anlagerung, bei der die Alkylenoxide gemeinsam zudosiert werden, möglich. Es ist auch möglich, bei der Herstellung der Polyetheralkohole sowohl block¬ weise als auch statistische Abschnitte in die Polyetherkette einzubauen.The addition of the alkylene oxides in the preparation of the polyether alcohols used for the process according to the invention can be carried out by the known processes. Thus, it is possible that the polyether alcohols contain only one alkylene oxide. When using a plurality of alkylene oxides, a so-called block-wise addition in which the alkylene oxides are added one after the other in succession, or a so-called statistical addition in which the alkylene oxides are added together, is possible. It is also possible to incorporate both blockwise and random sections into the polyether chain in the preparation of the polyether alcohols.
Die Anlagerung der Alkylenoxide erfolgt bei den dafür üblichen Bedingungen, wieThe addition of the alkylene oxides takes place under the customary conditions, such as
Temperaturen im Bereich von 60 bis 18O0C, bevorzugt zwischen 90 und 1400C, insbe¬ sondere zwischen 100 bis 13O0C und Drücken im Bereich von 0 bis 20 bar, bevorzugt im Bereich von 0 bis 10 bar und insbesondere im Bereich von 0 bis 5 bar. Die Mi¬ schung aus Startsubstanz und DMC-Katalysator kann vor Beginn der Alkoxylierung gemäß der Lehre von WO 98/52689 durch Strippen vorbehandelt werden.Temperatures in the range of 60 to 18O 0 C, preferably between 90 and 140 0 C, in particu lar between 100 to 13O 0 C and pressures in the range of 0 to 20 bar, preferably in the range of 0 to 10 bar and in particular in the range of 0 to 5 bar. The mixture of starting substance and DMC catalyst can be pretreated by stripping prior to the beginning of the alkoxylation according to the teaching of WO 98/52689.
Nach Beendigung der Anlagerung der Alkylenoxide wird der Polyetheralkohol zumeist nach üblichen Verfahren aufgearbeitet, indem die nicht umgesetzten Alkylenoxide so¬ wie leicht flüchtige Bestandteile entfernt werden, üblicherweise durch Destillation, Wasserdampf- oder Gasstrippen und oder anderen Methoden der Desodorierung. Falls erforderlich, kann auch eine Filtration erfolgen.After completion of the addition of the alkylene oxides, the polyether alcohol is usually worked up by customary processes by removing the unreacted alkylene oxides and volatile constituents, usually by distillation, steam or gas stripping and or other methods of deodorization. If necessary, filtration can also be carried out.
Der Katalysator kann nach Abschluss der Anlagerung der Alkylenoxide vom Reakti¬ onsgemisch abgetrennt werden. Es ist jedoch für die meisten Einsatzfälle der PoIy- etheralkohole, insbesondere bei der Herstellung von Polyurethanen, möglich, ihn im Produkt zu belassen.
In einer besonderen Ausführungsform kann die Herstellung der Polyetheralkohole auch kontinuierlich erfolgen. Eine solche Verfahrensweise ist beispielsweise in WO 98/03571 oder in JP H6-16806 beschrieben. Dabei werden in einen kontinuierli¬ chen Reaktor kontinuierlich Alkylenoxide und Startsubstanz dosiert und der entstehen- de Polyetheralkohol kontinuierlich entnommen.After completion of the addition of the alkylene oxides, the catalyst can be separated off from the reaction mixture. However, it is possible for most applications of polyether alcohols, especially in the production of polyurethanes, to leave it in the product. In a particular embodiment, the preparation of the polyether alcohols can also be carried out continuously. Such a procedure is described for example in WO 98/03571 or in JP H6-16806. In this process, alkylene oxides and starting substance are continuously metered into a continuous reactor and the resulting polyether alcohol is taken off continuously.
Die unter Verwendung von DMC-Katalysatoren hergestellten Polyetheralkohole wer¬ den, wie ausgeführt, zumeist zur Herstellung von Polyurethan-Weichschaumstoffen durch Umsetzung mit Polyisocyanaten verwendet.As stated, the polyether alcohols prepared using DMC catalysts are generally used for the production of flexible polyurethane foams by reaction with polyisocyanates.
Die nach dem erfindungsgemäßen Verfahren hergestellten DMC-Katalysatoren weisen in ihren Eigenschaften keine Nachteile gegenüber anderen, nach dem üblichen Batch- Verfahren hergestellten Katalysatoren auf. Durch das erfindungsgemäße Verfahren kann der Aufwand bei der Herstellung der DMC-Katalysatoren deutlich gesenkt wer- den. Außerdem weisen die nach dem erfindungsgemäßen Verfahren hergestellten DMC-Katalysatoren gleichbleibende Eigenschaften auf.The DMC catalysts prepared by the process according to the invention have no disadvantages in their properties over other catalysts prepared by the conventional batch process. By means of the method according to the invention, the expense in the production of the DMC catalysts can be significantly reduced. In addition, the DMC catalysts prepared by the process according to the invention have the same properties.
Die Erfindung soll an den nachfolgenden Beispielen näher erläutert werden.The invention will be explained in more detail in the following examples.
Beispiel 1 (Vergleich)Example 1 (comparison)
Semikontinuierliche Herstellung einer DMC-KatalysatorsuspensionSemicontinuous production of a DMC catalyst suspension
Lösung 1 bestand aus einer wässrigen Zinkacetat-Lösung (2,6 % Zink), Lösung 2 aus einer wässrigen Kaliumhexacyanocobaltat-Lösung mit 0,9 % Cobalt. In einen 3-Liter- Rührbehälter wurden Lösung 1 mit 7,91 kg/h und Lösung 2 mit 10 kg/h über eine Mischdüse dosiert. Beide Lösungen enthielten 2 Gew.-% eines oberflächenaktiven Mittels (Pluronic® PE6200 der BASF AG). Nach Befüllen des Rührkessels wurde die Zufuhr gestoppt und die vorliegende DMC-Suspension bei einer Temperatur von 200C im Rührbehälter und einem Energieeintrag durch Rühren von 1 W/l 1 h lang nachge- rührt. Anschließend wurde der Katalysator abfiltriert, mit Wasser gewaschen und bei 6O0C getrocknet.Solution 1 consisted of an aqueous zinc acetate solution (2.6% zinc), Solution 2 of an aqueous solution of potassium hexacyanocobaltate with 0.9% cobalt. Solution 1 at 7.91 kg / h and solution 2 at 10 kg / h were metered through a mixing nozzle into a 3 liter stirred tank. Both solutions contained 2 wt .-% of a surfactant (Pluronic PE6200 ® of BASF AG). After filling the stirred tank, the feed was stopped and the present DMC suspension stirred at a temperature of 20 0 C in the stirred tank and an energy input by stirring 1 W / l for 1 h. Subsequently, the catalyst was filtered off, washed with water and dried at 6O 0 C.
Beispiel 2Example 2
Kontinuierliche Herstellung einer DMC-Katalysatorsuspension über MischdüseContinuous production of a DMC catalyst suspension via mixing nozzle
Lösung 1 bestand aus einer wässrigen Zinkacetat-Lösung (2,6 % Zink), Lösung 2 aus einer wässrigen Kaliumhexacyanocobaltat-Lösung mit 0,9 % Cobalt. In einen 3-Liter- Rührbehälter wurden Lösung 1 mit 7,91 kg/h und Lösung 2 mit 10 kg/h kontinuierlich über eine Mischdüse dosiert. Beide Lösungen enthielten 2 Gew.-% eines oberflächen- aktiven Mittels (Pluronic® PE6200 der BASF AG). Nach Befüllen des Rührkessels wur¬ de weiter zudosiert, die vorliegende DMC-Suspension wurde bei einer Temperatur von 200C im Rührbehälter und einem Energieeintrag durch Rühren von 1 W/l füllstandsge-
regelt über ein Bodenablassventil kontinuierlich abgelassen. Die durchschnittliche Ver¬ weilzeit im Rührkessel betrug 10 min. Zur Sicherstellung des stationären Zustandes wurde der Versuch über 10 mittlere Verweilzeiten durchgeführt. Anschließend wurde der Katalysator abfiltriert, mit Wasser gewaschen und bei 6O0C getrocknet.Solution 1 consisted of an aqueous zinc acetate solution (2.6% zinc), Solution 2 of an aqueous solution of potassium hexacyanocobaltate with 0.9% cobalt. Solution 1 at 7.91 kg / h and solution 2 at 10 kg / h were metered continuously through a mixing nozzle into a 3 liter stirred tank. Both solutions contained 2 wt .-% of a surface-active agent (Pluronic ® PE6200 BASF AG). After filling the stirred tank wur¬ de dosed further, the present DMC suspension was at a temperature of 20 0 C in a stirred tank and an energy input by stirring 1 W / l füllstandsge- regulates via a bottom drain valve continuously drained. The average residence time in the stirred tank was 10 min. To ensure the steady state, the experiment was carried out over 10 mean residence times. Subsequently, the catalyst was filtered off, washed with water and dried at 6O 0 C.
Beispiel 3Example 3
Kontinuierliche Herstellung einer DMC-Katalysatorsuspension ohne MischdüseContinuous production of a DMC catalyst suspension without mixing nozzle
Lösung 1 bestand aus einer wässrigen Zinkacetat-Lösung (2,6 % Zink), Lösung 2 aus einer wässrigen Kaliumhexacyanocobaltat-Lösung mit 0,9 % Cobalt. In einen 3-Liter- Rührbehälter wurden Lösung 1 mit 3,95 kg/h und Lösung 2 mit 5 kg/h kontinuierlich über Einleitrohre dosiert. Beide Lösungen enthielten 2 Gew.-% eines oberflächenakti¬ ven Mittels (Pluronic® PE6200 der BASF AG). Nach Befüllen des Rührkessels wurde weiter zudosiert, die vorliegende DMC-Suspension wurde bei einer Temperatur von 35°C im Rührbehälter und einem Energieeintrag durch Rühren von 1 W/l füllstandsge¬ regelt über ein Bodenablassventil kontinuierlich abgelassen. Die durchschnittliche Ver¬ weilzeit im Rührkessel betrug 20 min. Zur Sicherstellung des stationären Zustandes wurde der Versuch über 10 mittlere Verweilzeiten durchgeführt. Anschließend wurde der Katalysator abfiltriert, mit Wasser gewaschen und bei 600C getrocknet.Solution 1 consisted of an aqueous zinc acetate solution (2.6% zinc), Solution 2 of an aqueous solution of potassium hexacyanocobaltate with 0.9% cobalt. Solution 1 at 3.95 kg / h and solution 2 at 5 kg / h were metered continuously via inlet tubes into a 3 liter stirred vessel. Both solutions contained 2 wt .-% of a oberflächenakti¬ ven agent (Pluronic ® PE6200 BASF AG). After filling the stirred tank was further metered in, the present DMC suspension was continuously discharged at a temperature of 35 ° C in a stirred tank and an energy input by stirring of 1 W / l Füllstandsge¬ regulated via a bottom drain valve. The average residence time in the stirred tank was 20 min. To ensure the steady state, the experiment was carried out over 10 mean residence times. Subsequently, the catalyst was filtered off, washed with water and dried at 60 0 C.
Vorschrift zur Ermittlung der Aktivität der KatalysatorenMethod for determining the activity of the catalysts
Zu 10 g eines Glycerinpropoxylats mit einem Molekulargewicht Mw von 1000 g/mol, im folgenden VP900 genannt, wurden die angegebenen Mengen des zu testenden DMC- Katalysators zugesetzt und die Mischung 5 Minuten mit einem Dispergiergerät TypTo 10 g of a glycerol propoxylate having a molecular weight Mw of 1000 g / mol, hereinafter called VP900, the indicated amounts of the DMC catalyst to be tested were added and the mixture for 5 minutes with a dispersing machine type
Ultra-Turrax® T25 der Fa. IKA zu einem Konzentrat dispergiert. Danach wurden weite¬ re 120 g VP900 zugesetzt und nochmals mit dem Ultra-Turrax® T25 5 Minuten lang homogenisiert. Danach wurde diese VP900/DMC-Mischung in einem Rührautoklaven 2 Stunden bei 1000C bei 3 mbar gehalten. Anschließend wurden bei 13O0C 70 g Propy- lenoxid auf einmal zudosiert. Aus dem Anstieg von Temperatur und Druck wurden die Maxima erfasst und als Anspringzeit und zugleich Wertung für die Aktivität registriert. Nach dem vollständigen Abreagieren des Propylenoxids, erkennbar an dem Absinken des Drucks auf ein konstantes Niveau, wurde der Polyetheralkohol nach einer Inertisie- rung mit Stickstoff aus dem Autoklaven abgelassen.
Ergebnisse:Ultra-Turrax® T25 from IKA dispersed to a concentrate. Thereafter, an additional 120 g of VP900 were added and homogenized again with the Ultra-Turrax® T25 for 5 minutes. Thereafter, this VP900 / DMC mixture was kept in a stirred autoclave for 2 hours at 100 0 C at 3 mbar. 70 g propylene oxide were then added at once at 13O 0 C. From the increase in temperature and pressure, the maxima were recorded and registered as a light-off time and at the same time rating for the activity. After complete reaction of the propylene oxide, recognizable by the drop in pressure to a constant level, the polyether alcohol was drained from the autoclave after inerting with nitrogen. Results:
Katalysator Konzentration [ppm] Anspringzeit [min] Pma/rmax Catalyst concentration [ppm] light-off time [min] P ma / r max
Beispiel 1 100 8 8,6bar/165°C Beispiel 2 100 7 8,9bar/175°CExample 1 100 8 8,6bar / 165 ° C Example 2 100 7 8,9bar / 175 ° C
Beispiel 3 100 10 8,4bar/169°CExample 3 100 10 8,4bar / 169 ° C
Vergleich* 100 8 8,6bar/172°CComparison * 100 8 8,6bar / 172 ° C
* EP862 997, Beispiel 1* EP862 997, Example 1
Wie ersichtlich, ist die katalytische Aktivität der nach dem erfindungsgemäßen Verfah¬ ren hergestellten DMC-Katalysatoren mit der von DMC-Katalysatoren aus herkömmli¬ chen Verfahren vergleichbar.
As can be seen, the catalytic activity of the DMC catalysts prepared by the process according to the invention is comparable to that of conventional DMC catalysts.
Claims
I . Kontinuierliches Verfahren zur Herstellung von DMC-Katalysatoren, dadurch gekennzeichnet, dass in einen kontinuierlich arbeitenden Reaktor die Lösungen eines Metallsalzes und einer Hexacyanometallatverbindung sowie gegebenen¬ falls organische Liganden und/oder organische Zusatzstoffe kontinuierlich zuge¬ führt werden und die entstehende Suspension der DMC-Verbindung dem Reak¬ tor kontinuierlich entnommen wird.I. Continuous process for the preparation of DMC catalysts, characterized in that in a continuously operating reactor, the solutions of a metal salt and a Hexacyanometallatverbindung and optionally organic ligands and / or organic additives are continuously zuge¬ leads and the resulting suspension of the DMC compound the Reak¬ gate is removed continuously.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass als kontinuierlich arbeitende Reaktoren Rührkesselreaktoren eingesetzt werden.2. The method according to claim 1, characterized in that stirred tank reactors are used as continuously operating reactors.
3. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass die Zuführung der Ausgangsverbindungen durch Einleitrohre erfolgt.3. The method according to claim 1, characterized in that the supply of the starting compounds is effected by inlet tubes.
4. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass die Einleitrohre auf die Oberfläche der Reaktionsmischung im Reaktor oder getaucht angebracht sind.4. The method according to claim 1, characterized in that the inlet pipes are mounted on the surface of the reaction mixture in the reactor or immersed.
5. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass die Zuführung der Ausgangsverbindungen über eine Mischdüse erfolgt.5. The method according to claim 1, characterized in that the supply of the starting compounds via a mixing nozzle.
6. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass die kontinuierliche Entnahme der Suspension aus dem Reaktor durch eine Füllstandsregelung, ge- koppelt mit einem Bodenventil, einem Abzug über eine Pumpe oder einem Über¬ lauf erfolgt.6. The method according to claim 1, characterized in that the continuous removal of the suspension from the reactor by a level control, coupled with a bottom valve, a trigger via a pump or an overflow takes place.
7. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass sich an die Entnah¬ me aus dem kontinuierlichen Reaktor eine Vorrichtung zum Zerkleinern der ge- bildeten Partikel anschließt.7. The method according to claim 1, characterized in that the removal from the continuous reactor is followed by a device for comminuting the particles formed.
8. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass die Umsetzung bei einer Temperatur von 10-80 0C durchgeführt wird.8. The method according to claim 1, characterized in that the reaction is carried out at a temperature of 10-80 0 C.
9. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass die mittlere Verweil¬ zeit im Reaktor im Bereich zwischen 1 und 180 Minuten liegt.9. The method according to claim 1, characterized in that the average residence time in the reactor is in the range between 1 and 180 minutes.
10. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass der Energieeintrag in den kontinuierlichen Reaktoren 10"2-10 kW/m3 beträgt.10. The method according to claim 1, characterized in that the energy input in the continuous reactors 10 "2 -10 kW / m 3 .
I 1. DMC-Katalysatoren, herstellbar nach einem der Ansprüche 1 bis 10. 1. DMC catalysts, preparable according to one of claims 1 to 10.
12. DMC-Katalysatoren nach Anspruch 11 , dadurch gekennzeichnet, dass sie kristallin sind.12. DMC catalysts according to claim 11, characterized in that they are crystalline.
13. DMC-Katalysatoren nach Anspruch 11 , dadurch gekennzeichnet, dass sie eine monokline Kristallstruktur aufweisen.13. DMC catalysts according to claim 11, characterized in that they have a monoclinic crystal structure.
14. Verwendung von DMC-Katalysatoren nach Anspruch 11 zur Anlagerung von Alkylenoxiden an Verbindungen mit aktiven.Wasserstoffatomen.14. Use of DMC catalysts according to claim 11 for the addition of alkylene oxides to compounds with active.hydrogen atoms.
15. Verfahren zur Herstellung von Polyetheralkoholen durch Anlagerung von Alky¬ lenoxiden an Verbindungen mit mindestens zwei mit Isocyanaten reaktiven Was¬ serstoffatomen unter Verwendung von Katalysatoren, dadurch gekennzeichnet, dass als Katalysatoren DMC-Katalysatoren nach Anspruch 11 eingesetzt wer¬ den. 15. A process for the preparation of polyether alcohols by addition of Alky¬ lenoxiden to compounds having at least two isocyanate-reactive hydrogen atoms using catalysts, characterized in that used as catalysts DMC catalysts according to claim 11.
Applications Claiming Priority (2)
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DE102004048735A DE102004048735A1 (en) | 2004-10-05 | 2004-10-05 | Process for the continuous production of DMC catalysts |
PCT/EP2005/010492 WO2006037541A2 (en) | 2004-10-05 | 2005-09-28 | Method for the continuous production of dmc catalysts |
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EP1799344A2 true EP1799344A2 (en) | 2007-06-27 |
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EP05789181A Withdrawn EP1799344A2 (en) | 2004-10-05 | 2005-09-28 | Method for the continuous production of dmc catalysts |
Country Status (8)
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US (1) | US20080071117A1 (en) |
EP (1) | EP1799344A2 (en) |
JP (1) | JP4954077B2 (en) |
KR (1) | KR20070063557A (en) |
CN (1) | CN101035617A (en) |
DE (1) | DE102004048735A1 (en) |
MX (1) | MX2007003684A (en) |
WO (1) | WO2006037541A2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011047780A1 (en) | 2009-10-19 | 2011-04-28 | Basf Se | Conditioning of double metal cyanide catalysts |
WO2011160797A1 (en) | 2010-06-23 | 2011-12-29 | Basf Se | Modified double metal cyanide catalysts, process for the preparation by treatment of crystalline dmc catalyst with bronsted acid and use thereof |
Families Citing this family (1)
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WO2011018471A1 (en) | 2009-08-13 | 2011-02-17 | Basf Se | Method for producing multimetal cyanide compounds |
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US3278458A (en) * | 1963-02-14 | 1966-10-11 | Gen Tire & Rubber Co | Method of making a polyether using a double metal cyanide complex compound |
JP2884614B2 (en) * | 1989-09-01 | 1999-04-19 | 旭硝子株式会社 | Method for producing double metal cyanide complex catalyst |
JP2570903B2 (en) * | 1990-11-27 | 1997-01-16 | 旭硝子株式会社 | Method for producing double metal cyanide complex catalyst |
US5158922A (en) * | 1992-02-04 | 1992-10-27 | Arco Chemical Technology, L.P. | Process for preparing metal cyanide complex catalyst |
US5891818A (en) * | 1997-07-31 | 1999-04-06 | Arco Chemical Technology, L.P. | Cyanide complex catalyst manufacturing process |
US6800583B2 (en) * | 1999-06-02 | 2004-10-05 | Basf Aktiengesellschaft | Suspension of multimetal cyanide compounds, their preparation and their use |
DE19958355A1 (en) * | 1999-12-03 | 2001-06-07 | Bayer Ag | Process for the production of DMC catalysts |
JP4909497B2 (en) * | 2001-05-10 | 2012-04-04 | アルベマーレ ネザーランズ ビー.ブイ. | Continuous process and equipment for efficient conversion of inorganic solid particles |
DE10228254A1 (en) * | 2002-06-24 | 2004-01-22 | Basf Ag | Process for the preparation of polyether alcohols |
JP4556496B2 (en) * | 2003-06-04 | 2010-10-06 | 旭硝子株式会社 | Double metal cyanide complex catalyst, production method thereof and use thereof |
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2004
- 2004-10-05 DE DE102004048735A patent/DE102004048735A1/en not_active Withdrawn
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2005
- 2005-09-28 KR KR1020077009163A patent/KR20070063557A/en not_active Application Discontinuation
- 2005-09-28 WO PCT/EP2005/010492 patent/WO2006037541A2/en active Application Filing
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- 2005-09-28 CN CNA2005800338252A patent/CN101035617A/en active Pending
- 2005-09-28 MX MX2007003684A patent/MX2007003684A/en unknown
- 2005-09-28 JP JP2007535062A patent/JP4954077B2/en not_active Expired - Fee Related
- 2005-09-28 EP EP05789181A patent/EP1799344A2/en not_active Withdrawn
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2011047780A1 (en) | 2009-10-19 | 2011-04-28 | Basf Se | Conditioning of double metal cyanide catalysts |
US9114380B2 (en) | 2009-10-19 | 2015-08-25 | Basf Se | Conditioning of double metal cyanide catalysts |
WO2011160797A1 (en) | 2010-06-23 | 2011-12-29 | Basf Se | Modified double metal cyanide catalysts, process for the preparation by treatment of crystalline dmc catalyst with bronsted acid and use thereof |
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US20080071117A1 (en) | 2008-03-20 |
WO2006037541A3 (en) | 2006-06-15 |
CN101035617A (en) | 2007-09-12 |
DE102004048735A1 (en) | 2006-04-27 |
KR20070063557A (en) | 2007-06-19 |
JP2008515617A (en) | 2008-05-15 |
JP4954077B2 (en) | 2012-06-13 |
WO2006037541A2 (en) | 2006-04-13 |
MX2007003684A (en) | 2007-05-21 |
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