CN1325165C - Process for continuously preparing double metal cyanide complex catalyst - Google Patents

Abstract

The present invention discloses a technology of a continuous method for preparing bimetal cyanide (DMC) catalysts. The steps for preparing the catalyst comprise material mix reaction, filtration, wash, water replacement, concentration, functional polymer addition in a continuous process. The catalyst adopts a three-stage drying step, and pulverization is carried out in the drying process. The catalyst used for synthesizing polyether glycol has the advantages of high reactivity, short induction period and very low unsaturation degree of the prepared polyether glycol, and the technology period of the present invention is within 36 hours.

Description

Process for continuously preparing double metal cyanide complex catalyst

Technical field

The present invention relates to double metal cyanide (DMC) complex catalyst manufacturing process

Background technology

As everyone knows, bimetallic cyanide complex catalyst (dmc catalyst) is used for epoxide ring-opening polymerization, and its composition is generally:

M _a ¹[M ²(CN) _b(G) _c] _dXM ³(X) _eWH ₂OyL ₁ZL ₂Formula I

M ¹Be that at least a metal ion is selected from: Zn ^(II), Fe ^(II), Fe ^(III), Co ^(II), Ni ^(II), Mo ^(IV), Sn ^(II), Cu ^(II), Pb ^(II), Mo ^(VI), Al ^(III), V ^(IV), v ^(V), Sr ^(II), W ^(VI), W ^(VI), Mn ^(II)And Cr ^(III)

M ²Be that at least a transition metal ions is selected from: Fe ^(II), Fe ^(III), Co ^(II), Co ^(III), Cr ^(II), Cr ^(III), Mn ^(II), Mn ^(III), V ^(IV), V ^(V), Ir ^(III), Rh ^(III), Ni ^(II), Ru ^(II)

M ³Represent M ¹And/or M ²

G, X are CN ^-, F ^-, Cl ^-, Br ^-, I ^-, OH ^-, NO ₂ ^-, CO ₃ ^2-, NO ₃ ^-, SO ₄ ^2-, CNO ^-, C ₂O ₄ ^2-, CNS ^-,

NCO ^-, NCS ^-And carboxylate radical RCOO ^-G, X can be identical or different

A, b, c, d, e are satisfied with positive and negative charge and equate

L ₁Represent water-soluble hetero atom organic complexing agent (complexant) as: alcohol, aldehyde, ketone, ether, ester, acid amides, nitrile, sulfide or its mixture, typically using the tert-butyl alcohol (TBA) to make complexant has been known technology.

L ₂Represent the functional polymer

Key reaction is by M ¹Water soluble salt at M ³(X) _eThere is (or adding proper time after reaction) down [M ¹Water soluble salt can equal M ³(X) _e] and M ²Cyanide alkali metal salt reaction (L is arranged in the solution ₁L ₂Can add at the appropriate time) generation double metal cyanide precipitation and accessory substance water-soluble alkali metal salts.Accessory substance and other excess water soluble salt must be removed before obtaining having active dmc catalyst.Nearly all dmc catalyst patent will state that all metal ion, acid ion etc. come from all being fit to of above-mentioned scope in its dmc catalyst, but embodiment meets following formula substantially:

Zn ₃[Co (CN) ₆] ₂XZnCl ₂WH ₂OyL ₁ZL ₂Formula II

L wherein ₁Basic is organic alcohol, L ₂Be the functional polymer

Zn wherein ₃[Co (CN) ₆] ₂Be by ZnCl ₂With alkali metal cyanide, be generally K ₃[Co (CN) ₆] reaction.Reaction equation is:

2K ₃[Co(CN) ₆]+3ZnCl ₂→Zn ₃[Co(CN) ₆] ₂↓+6KCl

Be reflected at L ₁Selectively be added with L ₂The aqueous solution in carry out accessory substance KCl and excessive ZnCl ₂By using L ₁L is selectively arranged ₂Aqueous solution cyclic washing remove, normally the reactant slurry- ^Separate→ " wet cake "-→ slurry repeatedly repeatedly, separation method generally all be filter, centrifugal, dialysis or topple over the method for supernatant liquor, add functional polymer L after washing is finished ₂After the certain hour strong agitation, be separated into " wet cake " again, obtain active DMC catalysts after the oven dry (pulverizing).

USP4843054 (Arco company) adds the filter aid particle in reactant mixture makes easy the separation, but active matter is diluted significantly, and this method is difficult to practical.L in the dmc catalyst of USP5158922 (Arco company) ₁Basic is Glyme (dimethoxy-ethane) or Diglyme (diethylene glycol dimethyl ether), does not have L ₂, emphasize M ³(X) _eSolution (30～75 ℃ of temperature) adds M ²The cyanide alkali metal salt soln in, think that such catalyst that order forms (cat) particle easily filters (agnogenio), slurry can filter immediately or place in the 24h, avoids excessive washing in the washing process in case unreacted M ³(X) _e(routine ZnCl ₂) excessive flush away, influence is active, slurry in the example- ^SeparateAfter → " the wet cake ", directly washing (not returning slurry form), air dry in normal temperature, the atmospheric air, their characteristics are catalyst crystalline state content height (＞35%), and are active low, are called as traditional dmc catalyst.The method of USP5470813 (Acro company) system dmc catalyst is in two steps: at first, water-soluble slaine and water-soluble metal cyanides salting liquid closely mix, at complexing agent L ₁Exist down to generate the mixture that contains the dmc catalyst precipitation, then, isolate dmc catalyst and carry out drying.Complexing agent can be included in earlier in one of them or the two kinds of solution, or precipitation adds after forming immediately, and the former is better.The method that reaches tight mixing has homogenizing, impact and mix, high shear stirring etc. makes amorphous catalyst, (crystalline state DMC compound＜1%wt), than the prepared high crystalline-state catalyst of simple agitation (crystalline state DMC compound＞35%M), when synthesizing polyether glycol, same 100ppm (final products relatively, as follows) time active big by 200% during active big 65%, 130～250ppm.Its dmc catalyst is made complexing agent with TBA among USP5482908 and the USP5536883 (Arco company), contains polyethers (M _n＞500), method for making is that first water-soluble metal salt and water soluble metal cyanide salt solution closely mix with homogenizer or high-shear impeller, in the presence of complexing agent (TBA), generate the mixture that contains the dmc catalyst precipitation, complexing agent can be included in earlier in one of them or the two kinds of solution, or add immediately after the precipitation formation, the former is better, then polyethers (M _n＞500) add in the formed slurry, use than low shearing speed and stir, think that undue agitation can make mixture thickened and cohesion, increase separating difficulty, the gained catalyst activity is reduced.Then by mode such as filter, centrifugal separate the back with 40～70%wt enveloping agent solution (polyethers that wherein preferably contains 2～8%wt) carry out slurry- ^Separate→ " wet cake "-→ mixture that the repeatedly cyclic washing of slurry is washed the available pure complexing agent in back or complexing agent and polyethers for the first time washes, at last vacuum (vacuum pressure-0.09～-0.1MPa) and 40～90 ℃ be dried to weight, this patent better method is to simplify washing process, needn't return slurry when promptly washing, directly washing " wet cake ", catalyst activity preferably: for example make PPOX trihydroxylic alcohol (M _n=6000) time, 100ppm, (under the 0.07MPa pressure) the 6.69kg expoxy propane of reaction rate in the time of 105 ℃ (PO)/gCo/min, degree of unsaturation 0.0042mol/kg.Dmc catalyst is made complexing agent with TBA among USP5545601 (corresponding CN application number 96119923), the USP5637673 (Arco company), contain 5～80%wt and have tert-hydroxyl group PPG, reaction and washing process are substantially with USP5482908 and USP5536883, this kind PPG that can contain 0.5～8%wt in the wash solution, catalyst vacuum (vacuum pressure-0.1MPa in the example, 50 ℃) be dried to weight, catalyst activity: make PPOX trihydroxylic alcohol (M _n=6000) time, with 70g PPOX trihydroxylic alcohol (M _n=700) make initiator, catalyst 100ppm, during 105 ℃ of reactions (reaction pressure 0.07MPa), maximum rate 29.4g PO/min, during gained polyethers degree of unsaturation 0.0043mol/kgUSP5891818 (Arco company) system dmc catalyst in view of in the former patent for making catalyst reach high activity, in the technology during high shear mixing reactor produce quite a large amount of foams, and certainly exist quite a large amount of low activity solids in the foam, impurities is flush away effectively, can not fully contact the complexing agent in the continuous phase again, and foam is easy to stick on the still wall again, thereby lowering productive rate and made catalyst activity reduces, so adopt reactant continuous phase sprayed into the reactor headroom circularly, thereby minimizing foam, further, built-in high shear mixer better effects if in the pipeloop (even still had been furnished with strong mixing apparatus originally) the particle that produces littler, active better, resulting in separation and the washing process " wet cake " contains 15～25%wt catalyst approximately, in pure complexing agent, form slurry again, solid content 10～30%wt, centrifugal or filter after carry out drying, whole production is washed in the cycle and solid/liquid separation accounted for for 80% time, owing to contain the impure mother liquor of 75～85%wt in " wet cake ", suitable pressure filtration makes solid content be increased to 50% before the washing, thereby minimizing washing times, institute's controlling catalyst is formed same USP5482908 in the example, system PPOX trihydroxylic alcohol (M _n=6000) time, 70g PPOX trihydroxylic alcohol (M _n=700) make initiator, catalyst 100ppm, reaction rate (under the 0.07MPa pressure) 31.0PO/min during 105 ℃ of reactions; Adopt spraying or freeze drying in USP5900384 and USP5998672 (Arco company) the system DMC cat technology, directly obtain the cat fine particle and do not need strong pulverizing, the gained catalyst stores is stable, when being used to make PPG, it is few that reactor stays dirt, and the product degree of unsaturation is low, narrow molecular weight distribution, think common commercial mass production technology 100h consuming time, wherein 88% time spends in separation, dry and pulverize, and in the crushing process particle surface is changed and cause active the reduction.This technology forms slurry by catalyst in the volatility complexing agent, comprise spraying or after freeze drying replaces common centrifugation and crushing process with non-clustered pattern, remove excessive complexing agent and directly obtain catalyst fines, technology 76h consuming time when every batch of output 135Kg (the common 108h that needs), in the example, K ₃[Co (CN) ₆] and ZnCl ₂After the strong hybrid reaction, through washing, centrifugation/return twice process of slurry again through freeze drying or spray-drying, the gained catalyst is relatively dry with conventional vacuum in TBA solution: freeze drying catalyst 25ppm under 130 ℃ of the reaction temperatures, gets M _n=8000 PPOX dihydroxylic alcohols, its degree of unsaturation 0.0061 (common law 0.0067) mol/Kg, polydispersity M _w/ M _nBe 1.19 (common laws 1.23), viscosity (25 ℃) 3940 (common law 4150) mpas; Spray dry gained cat makes M _n=6000 PPOX trihydroxylic alcohols (not giving condition), reaction rate 21.7 (common law 20.0) g PO/min, degree of unsaturation 0.0032 (common law 0.0034) mol/Kg.The made dmc catalyst of USP6204357 (Bayer company) is made complexant with TBA, contains functional polymer's cyclodextrin, and its catalyst comprises crystalline state, amorphous state or part crystalline state, stirs in the example and all uses at a high speed even matter mode, washs once, preferably catalyst example system M _nDuring=3800 PPOX dihydroxylic alcohols, with M _n=1000 PPOX dihydroxylic alcohols are made initiator, catalyst 20ppm, 105 ℃ of following induction time 197min, gained polyethers degree of unsaturation 0.008mol/kg.The made dmc catalyst of USP6291388 (Bayer company) is made complexant with TBA, contains functional polymer M _n＞500 polyethylene glycol oxide ether, its catalyst comprise crystalline state, amorphous state, part crystalline state again, stir and all use at a high speed even matter mode, and washing is still once, and in the example, the system hydroxyl value is the PPOX dihydroxylic alcohols (M of 29.8mgKOH/g preferably _n=3810), under 105 ℃ of reaction temperatures, cat 15ppm is with 50g PPOX dihydroxylic alcohols (M _n=1000) make initiator, total reaction time 395min, gained polyethers degree of unsaturation 0.011mol/kg, viscosity (25 ℃) 935mpas.

During the basic crystalline state type dmc catalyst of USP6323375 (Bayer company) system, TBA makes complexing agent, contains a kind of functional polymer in the catalyst, water 1～10%wt, water soluble salt (ZnCl ₂) 5～25%wt, all adopted at a high speed even matter mode in the embodiment, washing process for once, gained cat active testing in the comparatively ideal example: initiator M _n=1000 PPOX dihydroxylic alcohols 508,105 ℃ of reaction temperatures, cat 15ppm, induction time 80min, reaction time 335min, polyethers hydroxyl value 27.4mgKOH/g, viscosity 1084mpa.s (25 ℃).

Generally speaking, system during dmc catalyst by water-soluble metal salt (as ZnCl ₂) and water soluble metal cyanide (as K ₃[Co (CN) ₆]) reaction generation DMC, produced simultaneously accessory substance alkali metal salt (as KCl) is not have activity, must remove, generally all adopt separation such as pulp centrifuged, filtration, form wet cake, to be separated into the discontinuous method of wet cake behind the cleaning solution formation slurry again, repeatedly repeat, drying mode did not propose yet and can generally accept and the outstanding effect method simultaneously again.

Summary of the invention

The object of the invention is simplified the loaded down with trivial details process of washing methods at used intermittence when removing by-product impurities in the catalyst manufacturing process just, and solves the unsettled shortcoming of bringing thus of properties of product; Another purpose of the present invention solves the liquid level that strong mixed method is brought in the former patent of reactant mixture and produces a large amount of bubble-related issues; Another object of the present invention proposes effectively catalyst drying means.

(1) the present invention is directed to bimetallic cyanide complex catalyst and propose a kind of continuously preparing double metal cyanide (DMC) complex catalyst technology, comprise: 1. prepare the reaction mass hybrid reaction in the dmc catalyst process, the catalyst pulp filtration washing is removed by-product impurities, the moisture content displacement, concentrate, the functional polymer adds each step that waits formation catalyst overall structure requirement slurry and carries out with continuous process and finish; 2. above steps is to carry out the built-in kinetic pump of described every pipeline in a reactor that has membrane separation device and two or more pipeloops; 3. the slurry after above steps is finished is pressed into or filter by suction, carries out pressure filtration; 4. the pasty state catalyst that forms after the above-mentioned press filtration moves into the vacuum drier classification and is dried to constant weight, pulverizes and carries out during the course.

Wherein the catalyst general formula is: M _a ¹[M ²(CN) _b] _dXM ³(X) _cWH ₂OyTjPzA

Wherein:

M ¹Be that at least a metal ion is selected from: Zn ^(II), Fe ^(II), Fe ^(III), Co ^(II), Ni ^(II), Mo ^(IV), Sn ^(II), Cu ^(II), Pb ^(II), Mo ^(VI), Al ^(III), V ^(IV), V ^(V), Sr ^(II), W ^(IV), W ^(VI), Mn ^(II)And Cr ^(III)Preferentially be selected from Zn ^(II), Fe ^(III), Ni ^(II)In one or more, and with Zn ^(II)Be main.

M ²Be that at least a transition metal ions is selected from: Fe ^(II), Fe ^(III), Co ^(II), Co ^(III), Cr ^(II), Cr ^(III), Mn ^(II), Mn ^(III), V ^(IV), V ^(V), Ir ^(III), Rh ^(III), Ru ^(II), Ni ^(II)Preferentially be selected from Fe ^(III), Co ^(III), and with Co ^(III)Be main.

M ³Represent M ¹And/or M ²In one or more, preferred Zn ^(II)

X is for being selected from CN ^-, F ^-, Cl ^-, Br ^-, I ^-, OH ^-, NO ₂ ^2-, CO ₃ ^2-, NO ₃ ^-, SO ₄ ^2-, CNO ^-, C ₂O ₄ ^2-, CNS ^-, NCO ^-, NCS ^-And carboxylate radical RCOO ^-, preferred Cl ^-, SO ₄ ^2-In one or two, preferred Cl when selecting one of them ^-

A, b, c, d, e are satisfied with positive and negative charge and equate

T is selected from water-soluble hetero atom organic complexing agent as alcohol, aldehyde, ketone, ether, ester, acid amides, nitrile, sulfide or its mixture, preferred tertiary butanols (TBA), dimethoxy-ethane (Glyme), diethylene glycol dimethyl ether (Diglyme), tert-pentyl alcohol (TPA) preferably select the tert-butyl alcohol (TBA).

P is that PPG comprises PPOX, PPOX ethylene oxide copolymer polyalcohol, and its degree of functionality is 2～8, preferred 2～3 degrees of functionality, and molecular weight 500～10000, preferred 2000～4000,

X=0.1～10, w=0.1～1, y=0.1～1, (satisfy P content 0～5%wt) among the cat, A content 2～70%wt) among the cat (is satisfied in z=0.01～2.5 in j=0～0.15.

A is a kind of organosiloxane that contains the Si-C chain, its general molecular formula:

R wherein ₁, R ₂, R ₃, R ₄For being selected from methyl, ethyl, propyl group, butyl, R ₁, R ₂, R ₃, R ₄Can be identical or different.Molecular weight 300～6000, preferred 1000～4000.

After dmc catalyst manufacturing process is added with appropriate amount A, have the foam of attenuating to take place, catalyst pulp easily filters, and filters the outer easily oven dry of back pasty state catalyst, the easily effect of pulverizing.Gained activity and temperature tolerance obviously improve, and made PPG has utmost point low-unsaturation-degree, and A contains 2～70%wt in catalyst, preferred 5～50%wt, best 10～40%wt.P content can be limited to 0～5%wt, preferred 2～5%wt.

(2) technical process

A. water distribution dissolubility salt M ³(X) _cSolution is typically used ZnCl ₂, contain water-soluble hetero atom organic complexing agent, use the tert-butyl alcohol preferably, this organic complexing agent concentration range 10%～80%wt selectively contains P and/or A.P is 0.05～1%wt, and A is 0.1～5%wt.Water soluble salt M ³(X) _cConcentration range 10%～saturated.

B. join typically K of alkali metal hexacyanocobaltate acid salt ₃[Co (CN) ₆] solution, selectively be added with and contain water-soluble hetero atom organic complexing agent, use tert-butyl alcohol TBA preferably, this organic complexing agent concentration range 10%～80%wt, K ₃[Co (CN) ₆] solution concentration scope 1%～saturated, and selectively be added with K ₃[Fe (CN) ₆], measure and be K ₃[Co (CN) ₆] 0～20%wt, preferred 0～10%wt.

C. selectively in " a " solution be added to " b " on the contrary in solution or, M ³(X) _c/ K ₃[Co (CN) ₆] mass ratio is 1: 1～7: 1, be reflected in the reactor that has two or more pipeloops and carry out, every built-in high rotating speed kinetic pump of pipeline, rotating speed 1000～10000rpm.Material circulates at a high speed by pipeloop during reaction, generates M _a ¹[M ²(CN) _b] _d, typically be Zn ₃[Co (CN) ₆] ₂And water byproduct dissolubility sylvite, typically be KCl.

D. remove Zn ₃[Co (CN) ₆] ₂Other outer DMC compound is also selectively at Zn ₃[Co (CN) ₆] ₂Generate the back and add, other DMC compound of indication is: Ni ₃[Co (CN) ₆] ₂, Fe[Co (CN) ₆], Zn ₃[Fe (CN) ₆], Fe[Fe (CN) ₆], Ni ₃[Fe (CN) ₆] in one or more, the relative Zn of its total amount ₃[Co (CN) ₆] ₂Be 0～20%wt, preferred 0～10%wt.

E. utilize film device to carry out washing process after the reaction, film device places pipeloop, membrane aperture 0.1～50 μ m, the too small solution in aperture is difficult for passing through, and easily stopped up by catalyst fines, influence clean result, prolong the process time, cause catalyst activity to lower greatly, the excessive solution in aperture is very fast to be passed through, but catalyst fines also can partly run off, best 2～15 μ m of membrane aperture, byproduct of reaction and excess water soluble salt carry out continuous washing with film device, and slurry cycles through the film pipe under 0.1～0.4MPa pressure, water-soluble salt is discharged outside the film, and the DMC compound is still stayed in the film.For anti-fenestra is blocked, utilize regularly oppositely pressurization of Compressed Gas, used organic complexing agent concentration range 10%～80%wt in the washing process, the P that selectively contains 0.1%～5%wt A and 0.05%～1%wt in the cleaning solution, it is helpful to the slurry homogenizing to contain A, adds A and P and all improves helpful to catalyst activity.

F. washing finishes the back (to detect alkali metal ion, typically K in the parting liquid ⁺Concentration reaches below the 500ppm, below the preferred 300ppm, 200ppm is following for indicating better), replace part moisture content in the slurries with organic complexing agent, to water content＜20%wt, better＜15%wt, best＜5%wt, too much water content can make the dry difficulty of catalyst, also can influence the catalyst smashing capability; Then add P and A, addition should be greater than actual amount in the last catalyst, and is excessive at least 50%, and excessive part is P and the A amount that slurry is isolated in the solution to be had at last.With (660L/min) 0.5～5h that circulates at a high speed, best 1～3h.

G. carry out Separation of Solid and Liquid with spreading mass, available centrifugation, modes such as press filtration, the preferential employing of the present invention contains multimembrane pipe multi-bed filter, membrane aperture 2～15 μ m, and its advantage is can be to the outer slurry pressurization of film in the filter process, pressure 0.1～0.4MPa, and vacuumize in the film and combine the filter efficiency height; Another advantage can be to pressurizeing in the film, the cat that coats on the film pipe is come off and is unlikely to form and filters the barrier layer, and its overall merit is that filter area is big, and speed is fast, and is easy to operate, and controllability is strong, belongs to a kind of three-dimensional filter type.Obtain the pasty state catalyst of solid content 10～30%, preferred 15～25%.

H. pasty state cat is through 0～80 ℃ of following nature of temperature or negative pressure drying, preferably vacuum is drained, the preferential vacuum desiccator that adopts a kind of rotary built-in knife of the present invention, catalyst volatilization face constantly increases in its advantage dry run, thereby accelerates rate of drying, the preferential three step seasonings that adopt of the present invention, the first step, 0～30 ℃ of lower temperature, preferred 0～15 ℃, vacuum drying is to solid content 25～60%, and preferred 30～40%.In second step, 15～60 ℃, preferred 30～50 ℃ of vacuum drying are to solid content 40～95%, and preferred 60～90%.In the 3rd step, 40～80 ℃, preferred 45～65 ℃ of vacuum drying are to constant weight (catalyst is pulverized and finished in this process).

The invention effect

Remove by-product impurities with continuous processing in the cat manufacturing process of the present invention, overcome the unsettled shortcoming of properties of product that batch process brings thus; The present invention since material efficient circulation and be added with an amount of A in still solved the liquid level that strong mixed method is brought in the former patent of reactant mixture and produced a large amount of foams and make the active attenuating problem of final cat; The present invention proposes effectively catalyst drying means, avoids catalyst to cause the catalyst activity damage problem easily when common process is dry; Gained catalyst yield height of the present invention, technology is consuming time few, and the common process activity improves greatly relatively.

Technology gained catalyst of the present invention is used to make PPG, and is active high, and the gained PPG has ultralow degree of unsaturation, can reach 0.001～0.005mol/kg scope, when the system higher molecular weight such as M _n=6000～10000 o'clock, below the cat 30ppm, degree of unsaturation still can satisfy this scope.

Equipment therefor and drying means are applicable to any formula I Preparation of catalysts that satisfies in the technology of the present invention, and effect obviously improves.

Description of drawings

Fig. 1 is a catalyst pulp preparation technology schematic diagram

1, reaction: the reactant liquor that has prepared places reactor, and circulating at a high speed with the high speed kinetic pump by pipeloop generates DMC and accessory substance water-soluble alkali metal salts.

2, washing: byproduct of reaction and excess water soluble salt carry out continuous washing with membrane separation device, and slurry cycles through the film pipe by pump, and it is outer and DMC stays in the film that water-soluble salt is discharged film, for anti-fenestra is blocked, utilizes regularly oppositely pressurization of Compressed Gas.

3, displacement: replace part water in the slurry with organic complexing agent with the mode that washing is same.

4, add functional polymer A and P: same with reactive mode, circulation fully mixes with slurry at a high speed.

Fig. 2 catalyst pulp press filtration schematic diagram.Can combine to vacuumizing in outer slurry pressurization of film and the film in the pressure-filtering process.

The dry schematic diagram of Fig. 3 pasty state catalyst

Be one and have the vacuum drier that the pasty state catalyst is carried out refrigeration and heating temperature control, so that implement the three-stage drying method.

The specific embodiment

Embodiment 1 controlling catalyst Zn ₃[Co (CN) ₆] ₂ZnCl ₂0.5H ₂In the O0.15TBA0.015P0.092A one batching still, with 24kg ZnCl ₂Be dissolved in the 50L TBA/90L deionized water, be added in the reactor, in another batching still, 6kg K ₃[Co (CN) ₆] be dissolved in the 90L deionized water, a kind of solution in back is added in the reactor in the 30min, open Speed Circulation Pump simultaneously and carry out hybrid reaction, continue to enter the film circulation behind the circulation 1.5h, TBA and deionized water are made into 50% TBA solution (in add 0.1%A) and wash 5h (K in the detection eluate with 300L ⁺About 300ppm), displaces part moisture content in the slurry with the pure TBA 3h of 200L again, continue film and separate, be concentrated into slurry 300L (sampling records its filtrate water content 10%).Add 0.6kg PPOX trihydroxylic alcohol (M _n=3000) and 1.8kg A (M _n=2000), circulation 2h moves into slurry in the multimembrane pipe multi-bed filter, and the 7-8h press filtration is adopted three step seasonings till the solid content 16～20%, the first step, and 5～10 ℃, about 4.5h vacuum drying is to solid content 40%; In second step, 30～35 ℃, the 3h vacuum drying is to solid content 80%; In the 3rd step, 45～50 ℃, the 5.5h vacuum drying is to constant weight (cat is through pulverizing in the process).Get catalyst A

(pressing theoretical output yield) greater than 95%.About the total 36h consuming time of technology.

Comparative example 1 controlling catalyst Zn ₃[Co (CN) ₆] ₂ZnCl ₂0.5H ₂The raw materials used ratio of O0.15TBA0.015P0.092A is the same, but with batch process laboratory system: in the beaker, 24g ZnCl ₂Be dissolved in (solution 1) in the 50mL TBA/90mL deionized water, in another beaker, 6g K ₃[Co (CN) ₆] be dissolved in (solution 2) in the 90L deionized water, TBA and deionized water are made into 50% TBA solution (in add 0.1%A) with 300mL (solution 3), solution 1 is added in the solution 2, simultaneously with the even matter 2h reaction of homogenizer, isolate solid by 5 μ filters under the mixture pressure, solids cake compresses pulp 30min again under the even matter in 150mL solution 3 repeats this process and washes and (detect K in the filtered fluid after the same filtration ⁺300ppm is following), again at 300mL 10%TBA aqueous solution pulp again and add 0.6g PPOX trihydroxylic alcohol

(M _n=3000) and 1.8gA (M _n=2000), even matter 2h, press filtration to 18%, 50 ℃ of vacuum drying of solid content to constant weight, dry powder catalyst B 8.0g.

Comparative example 2

Dry preceding catalyst adopts comparative example 1 drying means in the example that takes a morsel 1, gets catalyst C.

Comparative example 3

With example 1 operation, but do not use A, washing extends to 6.5h and (detects K in the eluate ⁺About 300ppm), last P addition 2.4Kg gets cat D8.3Kg

Embodiment 3 system { Zn ₃[Co (CN) ₆] ₂+ 0.06Ni ₃[Co (CN) ₆] ₂+ 0.06Fe[Co (CN) ₆]) ZnCl ₂0.5H ₂O0.15TBA.0.015P0.092A

With embodiment 1, but ZnCl ₂Be 22Kg, K ₃[Co (CN) 6] is 5.5Kg, adds 0.33Kg Ni when washing begins when film separates ₃[Co (CN) ₆] ₂And 0.15Kg Fe[Co (CN) ₆] must catalyst E8.5Kg.

The system PPG

70g PPOX dihydroxylic alcohols (M _n=416), catalyst 8-30ppm (made relatively theoretical molecular polyalcohol) places the 2L autoclave pressure, stir down, temperature vacuumizes 30min under 105 ℃, removes micro-moisture, add the about 20g pressure of expoxy propane 0.07MPa, after pressure sharply descends, under the residual epoxide propane certain pressure, remain under certain reaction temperature and add, through the afterreaction phase to consume all expoxy propane in the still, take out volatile matter for 90 ℃, obtain polyalcohol, carry out hydroxyl value, double bond content, mensuration such as viscosity.

Example A is with catalyst A (15ppm) system PPOX dihydroxylic alcohols (M _n=4000)

With above-mentioned steps, 105 ℃, make polyalcohol under the 0.07Mpa, the result is as follows:

Induction period (min): 55

Total reaction time (min): 300

Maximum reaction rate (g PO/min): 10

Polyalcohol:

Hydroxyl value (mg KOH/g): 29.1

Double bond content (mol/Kg): 0.0040

Viscosity (25 ℃, mpas): 950

Comparative examples A (1) is with catalyst B, and condition is the same, and the result is as follows:

Induction period (min): 160min

Total reaction time (min): 510

Maximum reaction rate (g PO/min): 5g/min

Polyalcohol:

Hydroxyl value (mg KOH/g): 30.50

Double bond content (mol/Kg): 0.0085

Viscosity (25 ℃, mpas): 1450

Comparative examples A (2) is with catalyst C, and condition is the same, and the result is as follows:

Induction period (min): 65

Total reaction time (min): 340

Maximum reaction rate (g PO/min): 9.0g/min

Polyalcohol:

Hydroxyl value (mg KOH/g): 29.20

Double bond content (mol/Kg): 0.0045

Viscosity (25 ℃, mpas): 1020

Comparative examples A (3)

With catalyst D, condition is the same, and the result is as follows:

Induction period (min): 130min

Total reaction time (min): 450

Maximum reaction rate (g PO/min): 6.0g/min

Polyalcohol:

Hydroxyl value (mg KOH/g): 30.0

Double bond content (mol/Kg): 0.0080

Viscosity (25 ℃, mpas): 1350

Embodiment

With catalyst E, condition is the same, and the result is as follows:

Induction period (min): 40mia

Total reaction time (min): 240

Maximum reaction rate (g PO/min): 12g/min

Polyalcohol:

Hydroxyl value (mg KOH/g): 28.1

Double bond content (mol/Kg): 0.0015

Viscosity (25 ℃, mpas): 757

Continuous process stability example of the present invention

With embodiment 1 processing step, system different batches catalyst is by routine A system PPOX dihydroxylic alcohols (M _n=4000) result is as follows:

Batch process laboratory controlling catalyst batch stable comparative example

With comparative example 1 processing step system different batches catalyst, by routine A system PPOX dihydroxylic alcohols (M _n=4000) result is as follows:

Claims (17)

1, a kind of process for continuously preparing double metal cyanide complex catalyst, it is characterized in that: 1) the reaction mass hybrid reaction in the preparation dmc catalyst process, the catalyst pulp filtration washing is removed by-product impurities, the moisture content displacement, concentrate, the functional polymer adds and forms the catalyst overall structure, and each step of requirement processing slurry is carried out with continuous process and finished; 2 above stepss are to carry out every built-in kinetic pump of pipeloop in a reactor that has membrane separation device and two or more pipeloops; 3) slurry after above steps is finished is pressed into or filter by suction, carries out pressure filtration; 4) the pasty state catalyst that forms after the above-mentioned press filtration moves into the vacuum drier classification and is dried to constant weight, pulverizes and carries out during the course.

2, technology according to claim 1 is characterized in that this bimetallic cyanide complex catalyst satisfies following general formula:

M _a ¹[M ²(CN) _b] _d·xM ³(X) _c·wH ₂O·yT·jP·zA

Wherein,

M ¹Be at least a metal ion, be selected from: Zn ^(II), Fe ^(III), Ni ^(II)In one or more,

M ²Be at least a transition metal ions, be selected from: Fe ^(III), Co ^(III),

M ³Be at least a metal ion, be selected from: Zn ^(II), Fe ^(III), Ni ^(II)In one or more,

X is selected from Cl ^-, SO ₄ ^2-In one or two,

A, b, c, d satisfy positive and negative charge and equate,

T is the tert-butyl alcohol,

P is a PPG, is selected from PPOX, PPOX ethylene oxide copolymer polyalcohol, and its degree of functionality is 2～8, molecular weight 500～100000,

A is a kind of organosiloxane that contains the Si-C chain, satisfies following general formula:

R wherein ₁, R ₂, R ₃, R ₁Be alkyl, be selected from methyl, ethyl, propyl group, butyl, R ₁, R ₂, R ₃, R ₁Can be identical or inequality; The molecular weight of described A is 300～6000;

X=0.1～10, w=0.1～1, y=0.1～1, P content 0～5%wt in the DMC catalysts is satisfied in j=0～0.15, and A content 2～70%wt in the DMC catalysts is satisfied in z=0.01～2.5.

3, technology according to claim 1 is characterized in that the even mixing of the reaction mass that carries out in the reactor is reactor bottom material to be extracted out by Speed Circulation Pump place reactor top to come reciprocation cycle to finish.

4, technology according to claim 1 is characterized in that washing and filtering is by circular route coarse particles to be pumped into membrane separation device to isolate filtrate with tert-butyl alcohol solution washing after the described mixing of claim 3 is finished, and treats K in the eluate ^-1Washing is finished during smaller or equal to 300ppm.

5, as technology as described in the claim 4, the concentration of the tert-butyl alcohol aqueous solution of using when it is characterized in that washing is 10～99%.

6, as technology as described in claim 4 or 5, it is characterized in that the used tert-butyl alcohol aqueous solution contains the A of 0.1～5% concentration.

7, technology according to claim 1 is characterized in that used displacer adopts tert-butyl alcohol concentration more than or equal to 80% in displacement moisture content step, o'clock finishes to slurry water content＜25%.

8, technology according to claim 1, it is characterized in that in reactor, finishing add functional polymer P and A after, evenly mix by circular route circulation back.

9,, it is characterized in that in the Speed Circulation Pump that adopts the volume of material per minute by pump and material cumulative volume are than for more than or equal to 1: 2 as technology as described in the claim 3.

10, as technology as described in the claim 1,3, one of 4, it is characterized in that membrane aperture is 0.1～50 μ m in the used membrane separation device.

11, technology according to claim 1 is characterized in that moving into filter at slurry filters, and slurry leaches filtrate to solid content 10～30%.

12, technology according to claim 1 is characterized in that adopting a kind of vacuum drier of rotary built-in knife in process of vacuum drying.

13,, it is characterized in that in process of vacuum drying, adopting three grades of boulton process, 0～30 ℃ of first order low temperature as technology as described in claim 1 or 12; 15～60 ℃ of the second level; 40～80 ℃ of the third level.

14,, it is characterized in that every period termination time is: the first order is to solid content 25～60% at three grades of boulton process that adopt as technology as described in the claim 13; The second level is to solid content 40～95%; The third level is dried to constant weight.

15, as technology as described in the claim 2, it is characterized in that M among the A in the bimetallic cyanide complex catalyst ²Be Co ^(m)

16, as technology as described in the claim 2, it is characterized in that M among the A in the bimetallic cyanide complex catalyst ³Be Zn ^(II)

17, as technology as described in the claim 2, it is characterized in that the X in the bimetallic cyanide complex catalyst is Cl ^-

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