CN106582055B - A kind of preparation method of application and blocked isocyanate of the solvent separation equipment in blocked isocyanate crystal separates dissolving agent process - Google Patents
A kind of preparation method of application and blocked isocyanate of the solvent separation equipment in blocked isocyanate crystal separates dissolving agent process Download PDFInfo
- Publication number
- CN106582055B CN106582055B CN201611101581.3A CN201611101581A CN106582055B CN 106582055 B CN106582055 B CN 106582055B CN 201611101581 A CN201611101581 A CN 201611101581A CN 106582055 B CN106582055 B CN 106582055B
- Authority
- CN
- China
- Prior art keywords
- crystal
- solvent
- slurry
- blocked isocyanate
- load bearing
- 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.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0018—Evaporation of components of the mixture to be separated
- B01D9/0031—Evaporation of components of the mixture to be separated by heating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0018—Evaporation of components of the mixture to be separated
- B01D9/0027—Evaporation of components of the mixture to be separated by means of conveying fluid, e.g. spray-crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/08—Separation; Purification; Stabilisation; Use of additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D2009/0086—Processes or apparatus therefor
Abstract
Application and blocked isocyanate preparation method of a kind of solvent separation equipment of the present invention in blocked isocyanate crystal separates dissolving agent process, belong to isocyanates preparing technical field.The present invention heats in the state of completely cutting off air in closed container to crystal, the solvent release crystal in heating process in crystal, and solvent heating keeps geo-stationary between crystal crystal grain during departing from crystal, crystal is separated with solvent；Blocked isocyanate particle is prepared after described crystal separation solvent.The present invention is separated crystal with solvent by directly heating, and is significantly reduced the use ratio of solvent, is improved the precipitation efficiency of crystal；The centrifugal separation processes of crystal and mother liquor are avoided, eliminate harm of the solvent to environment.
Description
Technical field
The invention belongs to isocyanates preparing technical field, is being closed more specifically to a kind of solvent separation equipment
The preparation method of application and blocked isocyanate in isocyanates crystal separation dissolving agent process.
Background technology
Monoisocyanates is the important intermediate of organic synthesis, can be made into a series of carbamate insecticides, sterilization
Agent, herbicide, it is also used for improving the water proofing property of plastics, fabric, leather etc..Isocyanate-monomer is poisonous, unsaturated containing height
The isocyanate groups (- NCO, structural formula-N=C=O) of double bond, thus chemical property is very active.- N=C=O tries with nucleophilic
Agent has a higher reactivity, very active under the system normal temperature, can not exist with single group form-separating, it has to easy phase
The component of mutual reactance separates, and remixes together during use.4,4, the property and isocyanide of-'-diphenylmethane diisocyanate (MDI)
Acid esters relatively, therefore MDI monomer need it is stored refrigerated, the shelf-life is short, it is easy to autohemagglutination formed dimer, tripolymer, poly
Body, so as to influence its activity；Before polyurethane binder solidification to the moisture in the raw materials such as solvent, resin and live air very
Sensitivity, in isocyanates (- NCO) group can with the active H reaction generation sulfonylureas in water, to polyurethane adhesive and coating
Application bring many difficulties.In order to temporarily suppress poison, the secondary negative consequence that its active zone comes before use, allow in isocyanates
(- NCO) group is temporarily lost with activity, it is normally preserved at normal temperatures, can be same without worrying that it is rotten, during processing
Water and other raw materials containing active H mix, and without worrying that it can react, manufactured adhesive can be protected for a long time
Deposit, conventional method is that MDI is closed using end-capping reagent caprolactam in the art, and this isocyanates being closed can
To be processed and preserve under normal temperature and water and various ambient containing hydrogen states, when needing to use the activity of the isocyanates, apply
Adding certain condition (heating, catalyst), the chemical bond between end-capping reagent and active group (- NCO) will be broken, discharge again (-
NCO) active group, so as to recover the activity of isocyanates.
On the preparation technology of caprolactam blocked isocyanate, existing Patents disclose.For example, Chinese patent application
Number it is 200810026947.4, publication date is that in August, 2008 patent application document of 27 days discloses a kind of high stability in oneself
The preparation method of amido end-blocking isocyanate binder emulsion, comprises the following steps：(1) vacuum takes off caprolactam at normal temperatures
Water, toluene distill water removal after adding molecular sieve；(2) dried caprolactam and toluene wiring solution-forming are added into band stirring, condensation
In the three-necked bottle of device, the toluene solution of 4,4- '-diphenylmethane diisocyanates is added dropwise, it is white obtained by reaction in the case where there is nitrogen protection
Color solid is washed with water, and 4, the 4- '-diphenylmethane diisocyanates of caprolactam blocking are obtained after vacuum drying；(3) by caprolactam
End-blocking 4,4- '-diphenylmethane diisocyanates white solid is milled in advance, and that main stabilizer, viscosity regulation are added after 7-15 minutes is steady
Determine agent, defoamer and water, 1.5-2.5 hours of the milling milk-white coloured suspension of scattered gained is adhesive agent emulsion.Chinese patent
Application No. 201010242879.2, Shen Qing Publication open day be the patent application document of on 01 19th, 2011 disclose it is a kind of oneself
Lactams closing methyl diphenylene diisocyanate monomer addition product and preparation method thereof, using caprolactam under certain conditions
Closed isocyanic ester monomer, so as to which the caprolactam for obtaining to be stabilized at normal temperatures closes diphenylmethane diisocyanate
Ester monomer addition product and preparation method thereof, the monomer addition product, the raw material comprising following parts by weight are prepared：Caprolactam 1-
20 parts, methyl diphenylene diisocyanate 1-25 parts, ethyl acetate or xylene solvent 70-120 parts are insoluble by gained after reaction
Property addition product separated from solvent, obtain powdery caprolactam closing methyl diphenylene diisocyanate monomer addition product.
Although above-mentioned patent application is improved to existing production technology, often simply to existing production stage
Improved, be but difficult to break existing technological process from production procedure and realize that core technology is changed, and lacked special
Solvent separation equipment applied to blocked isocyanate crystal so that solvent separation process in blocked isocyanate preparation process
Complexity, the low separation efficiency of solvent, have a strong impact on the production efficiency of blocked isocyanate.
The content of the invention
1. to solve the problems, such as
The problem of for the solvent separation process complexity in existing isocyanates preparation process, the low separation efficiency of solvent,
The present invention provides application and closing isocyanide of a kind of solvent separation equipment in blocked isocyanate crystal separates dissolving agent process
The preparation method of acid esters；Wherein：
Application of a kind of solvent separation equipment provided in blocked isocyanate crystal separates dissolving agent process, by molten
Agent separation equipment, can simplify the separation process of crystal, and improve the separative efficiency of solvent；Solvent can also further be avoided
Volatilize and pollute environment；Condensing unit with bonding solvent, the rate of recovery and recovery purity of solvent can also be further improved, with drop
Low production cost；
The blocked isocyanate preparation method of solvent is provided under a kind of crystal grain relative static conditions provided, envelope can be simplified
The solvent separating step of isocyanates preparation process is closed, improves the separative efficiency of solvent, and improves the production of blocked isocyanate
Efficiency；The solvent use ratio in isocyanates preparation process can further be reduced；Condensation removal process with bonding solvent, enters
One step can also improve the rate of recovery and recovery purity of solvent, to reduce production cost.
2. technical scheme
In order to solve the above problems, the technical solution adopted in the present invention is as follows：
A kind of solvent separation equipment for blocked isocyanate crystal of the present invention, including isolation air element, should
Isolation air element is used to completely cut off influence of the air to crystal pulp separation dissolving agent process；Crystal load bearing unit, the crystallization
Thing load bearing unit is used to keep to carry out heating separation solvent in the state of geo-stationary between crystal crystal grain；Heating unit,
The heating unit is used to provide thermal source for crystal pulp separation solvent.
Crystal load bearing unit is transmission load bearing component or fixes load bearing component, the transmission load bearing component and fixed supporting part
Part is used to carry crystal slurry.
Described transmission load bearing component is conveyer belt, and during conveyer belt moves, crystal slurry uniformly fills paving
In the surface of conveyer belt, the dress of crystal slurry serialization on a moving belt spreads and heats separation solvent.
Described transmission load bearing component is reciprocating loading plate, during loading plate moves back and forth, crystal slurry
The uniform dress of material is laid on the surface of loading plate so that crystal slurry heats separation solvent on loading plate.
Isolation air element includes closed container and air extractor, and wherein crystal load bearing unit is arranged at closed container
Interior, closed container provides enclosed environment for crystal slurry drying, and the gas in closed container is extracted out and built by air extractor
Vacuum environment.
Isolation air element includes closed container and protective gas feeder, and wherein crystal load bearing unit is arranged at close
Close in container, closed container separates solvent for crystal and provides enclosed environment, and protective gas feeder supplies to closed container
Influence of the air to crystal slurry drying process is completely cut off to protective gas；Described protective gas is N2、CO2Or indifferent gas
One or more kinds of mixtures in body.
Also include slurry adding apparatus, the slurry adding apparatus is used to crystal slurry dress being laid on crystal load bearing unit
Surface；Particle collection device, the particle collection device are used to crystallize composition granule after accepting separation solvent；Described powder collection dress
Setting in the bottom of crystal load bearing unit, and particle collection device is arranged at one end away from slurry adding apparatus；Described
Heating unit is heater or high-temperature gas.
Also include slurry adding apparatus, the slurry adding apparatus is used to crystal slurry dress being laid on crystal load bearing unit
Surface；Particle collection device, the particle collection device are used to crystallize composition granule after accepting separation solvent；Solvent condensing device, should
Solvent condensing device, which is used to condense solvent, to be reclaimed；Described particle collection device is located at the bottom of crystal load bearing unit, and
Particle collection device is arranged at one end away from slurry adding apparatus；Described heating unit is heater, described solvent
Condensing unit is connected through air extractor with closed container.
Or also including slurry adding apparatus, the slurry adding apparatus is used to crystal slurry dress being laid on crystal carrying
Cell surface；Particle collection device, the particle collection device are used to crystallize composition granule after accepting separation solvent；Solvent condensation dress
Put, the solvent condensing device, which is used to condense solvent, to be reclaimed；Described particle collection device is located under crystal load bearing unit
Portion, and particle collection device is arranged at one end away from slurry adding apparatus；Described heating unit is heater or high temperature
Gas, described solvent condensing device are connected with closed container.
The blocked isocyanate preparation method of solvent, step 1 are separated under the crystal grain relative static conditions of the present invention：Will be molten
Agent, sealer, isocyanate-monomer synthesize and separate out crystal；Step 2：To crystal slurry in the state of air is completely cut off
Heated, the solvent release crystal in heating process in crystal slurry, solvent heating is protected during departing from crystal
Geo-stationary between crystal crystal grain is held, crystal pulp separation solvent is obtained blocked isocyanate particle.
By crystal slurry as carrying out heating separation solvent on transmission load bearing component or fixed load bearing component in step 2.
Described transmission load bearing component is conveyer belt, and during conveyer belt moves, crystal slurry uniformly fills paving
In the surface of conveyer belt, the dress of crystal slurry serialization on a moving belt spreads and heats separation solvent；Or described transmission
Load bearing component is reciprocating loading plate, and during loading plate moves back and forth, uniformly dress is laid on carrying to crystal slurry
The surface of plate so that crystal slurry heats separation solvent on loading plate.
The addition of solvent is 1-4L/ isocyanate-monomers kg during synthetically prepared isocyanates in step 1.
The solid content of crystal slurry is 35%-65% in step 2, the dress paving thickness in crystal slurry heating process
For 1-15mm.
The state for completely cutting off air in step 2 is that vacuum environment is built in closed container or is full of in closed container
Protective gas, described protective gas are N2、CO2Or one or more kinds of mixtures in inert gas.
Thermal source is provided for the heating of crystal slurry by heater in step 2, described heater has 2-8
Bringing-up section, the heating-up temperature that bringing-up section is radiated to crystal slurry are 40-180 DEG C.
Thermal source is provided for the heating of crystal slurry by high-temperature gas in step 2, described high-temperature gas is the guarantor of high temperature
Gas is protected, the temperature of high-temperature gas is 40-180 DEG C.
3. beneficial effect
Compared to prior art, beneficial effects of the present invention are：
(1) a kind of solvent separation equipment for blocked isocyanate crystal of the invention, directly by reacted knot
Brilliant thing slurry is as on the crystal load bearing unit in closed container so that crystal slurry between crystal crystal grain is kept
Heating separation solvent is carried out in the state of geo-stationary, simplifies the separation process of crystal, and improve the separative efficiency of solvent；
(2) a kind of solvent separation equipment for blocked isocyanate crystal of the invention, in isolation air element
Heating separation solvent, and by solvent condensing device can by solvent condense reclaim, avoid solvent volatilize and pollute the same of environment
When, improve the rate of recovery of solvent and reclaim purity, so as to reduce production cost；
(3) a kind of solvent separation equipment for blocked isocyanate crystal of the invention, conveyer belt or carrying are selected
Plate as transmission load bearing component, realize crystal continuous production, maintain again brilliant thing slurry keep crystal crystal grain it
Between heating separation solvent is carried out in the state of geo-stationary, so as to improve the solvent separative efficiency of crystal and full-range
Production efficiency；
(4) a kind of solvent separation equipment for blocked isocyanate crystal of the invention, slurry adding apparatus can incite somebody to action
Crystal slurry is uniformly layered on crystal load bearing unit, improves the laying efficiency and the quality of production of crystal slurry, and carries
The high separative efficiency of solvent；
(5) a kind of solvent separation equipment for blocked isocyanate crystal of the invention, closed container is used as knot
Brilliant thing slurry drying provides enclosed environment, and the gas in closed container is extracted out and builds vacuum environment by air extractor, so that every
Exhausted air avoids environmental pollution and production hidden danger to the influence in crystal drying process；
(6) a kind of solvent separation equipment for blocked isocyanate crystal of the invention, closed container is used as knot
Brilliant thing separation solvent provides closed environment, and protective gas feeder has completely cut off air pair to closed container supply protective gas
The influence of crystal slurry drying process, avoid environmental pollution and production hidden danger；
(7) the blocked isocyanate preparation method of solvent is separated under a kind of crystal grain relative static conditions of the invention, is being protected
Hold between crystal crystal grain under relative static conditions, the solvent release crystal in heating process in crystal slurry, realize
The one-step method of crystal and crystal grain removes, and eliminates the centrifugal separation processes of crystal and mother liquor, and avoid crystal and exist
Discharged during centrifugation with the centrifugation of solvent, while the separative efficiency of solvent is improved, also improve envelope
Close the production efficiency of isocyanates；
(8) the blocked isocyanate preparation method of solvent is separated under a kind of crystal grain relative static conditions of the invention, is passed through
Heating separation solvent is carried out to crystal under plateau, crystal grain is in all the time during ensure that crystal separation container
Relative static conditions, avoid crystal that crystal formation change occurs during solvent is separated, so as to ensure that blocked isocyanate
The quality of production of particle；
(9) the blocked isocyanate preparation method of solvent is separated under a kind of crystal grain relative static conditions of the invention, significantly
Improve the acceptance level to crystal slurry concentration so that the solid content of the crystal slurry in production process is by 20%-
30% brings up to 35-65%, reduces the use ratio of solvent, and has saved the production cost of blocked isocyanate particle；
(10) the blocked isocyanate preparation method of solvent, heating are separated under a kind of crystal grain relative static conditions of the invention
Device has 2-8 bringing-up section, and the heating-up temperature that bringing-up section is radiated to crystal slurry is 40-180 DEG C；Or high-temperature gas is
The heating of crystal slurry provides thermal source, and the temperature of high-temperature gas is 40-180 DEG C, so as to ensure that crystal slurry is empty in isolation
Fully heating separates solvent under conditions of gas, and ensure solvent is sufficiently disengaged from crystal；
(11) the blocked isocyanate preparation method of solvent, crystallization are separated under a kind of crystal grain relative static conditions of the invention
Dress paving thickness in thing slurry heating process be 1-15mm, so as to ensure to separate solvent during solvent is abundant, efficiently separates.
Brief description of the drawings
Fig. 1 is the overall structure diagram of separation equipment of the present invention；
Fig. 2 is the structural representation of the embodiment 2 of separation equipment of the present invention；
Fig. 3 is the structural representation of the embodiment 3 of separation equipment of the present invention；
Fig. 4 is that the loading plate of the embodiment 3 of separation equipment of the present invention moves to the structural representation of left end；
Fig. 5 is the structural representation of the embodiment 4 of separation equipment of the present invention；
Label declaration in accompanying drawing：
110th, closed container；120th, air extractor；130th, protective gas feeder；
210th, load bearing component is transmitted；220th, fixed load bearing component；
310th, heater；320th, gas heater block is protected；
410th, particle collection device；
510th, slurry adding apparatus；520th, solvent condensing device.
Embodiment
Accompanying drawing hereafter with reference to the detailed description of the exemplary embodiment of the present invention, the accompanying drawing forms one of description
Point, show the enforceable exemplary embodiment of the present invention as example in the figure.Although these exemplary embodiment quilts
Fully describe in detail to enable those skilled in the art to implement the present invention, it is to be understood that can realize other embodiment and
Can without departing from the spirit and scope of the present invention to the present invention various changes can be made.Hereafter to embodiments of the invention
More detailed description is not limited to required the scope of the present invention, and just to be illustrated and do not limit pair
The description of the features of the present invention and feature, to propose to perform the best mode of the present invention, and it is sufficient so that those skilled in the art
The present invention can be implemented.Therefore, the scope of the invention is only defined by the appended claims.
Hereafter detailed description of the present invention and example embodiment can be more fully understood with reference to accompanying drawing, wherein the present invention
Element and feature are identified by reference.
Embodiment 1
As shown in Figure 1：A kind of solvent separation equipment for blocked isocyanate crystal of the present invention, including isolation are empty
Gas unit, crystal load bearing unit and heating unit.Wherein, isolation air element includes closed container 110 and air extractor
120, above-mentioned crystal load bearing unit is arranged in closed container 110, and closed container 110 provides envelope for crystal slurry drying
Gas in closed container 110 is extracted out and builds vacuum environment by closed loop border, air extractor 200；Completely cut off air element be used for every
Exhausted influence of the air to crystal pulp separation dissolving agent process.Described crystal load bearing unit is transmission load bearing component 210, is passed
Load bearing component 210 is sent to be used to keep to carry out heating separation solvent in the state of geo-stationary between crystal crystal grain.Described
Heating unit is heater 310, and the heater 310 is used to provide thermal source for crystal pulp separation solvent.
Transmission load bearing component 210 is provided with closed container 110, one end of described transmission load bearing component 210 is provided with
Slurry adding apparatus 510, the slurry adding apparatus 510 are high-pressure pump, and crystal slurry can be delivered to closed container by high-pressure pump
In 110, and fill and be laid on transmission load bearing component 210 surface, transmission load bearing component 210 is close to one end of slurry adding apparatus 510
For feed end；The other end of transmission load bearing component 210 is provided with particle collection device 410, and transmission load bearing component 210 is close to particle
One end of collection device 410 is discharge end.
It is worth further illustrating, above-mentioned transmission load bearing component 210 accommodates or filled the surface of paving crystal slurry
It can be done relative motion relative to slurry adding apparatus 510 so that crystal slurry can be filled and be laid on biography by slurry adding apparatus 510
The surface of load bearing component 210 is sent, smooth, uniform crystal slurry dress laying is formed, so as to be advantageous to filling for crystal slurry
Divide, be synchronous dry.As shown in figure 1, the transmission load bearing component 210 can be conveyer belt, described conveyer belt is with traction piece
Conveyor equipment, such as ribbon conveyer, apron conveyor etc., under the driving of conveyer belt actuating unit, conveyer belt carrying
The surface of crystal slurry can do relative motion relative to slurry adding apparatus 510, so as to which crystal slurry is uniformly filled into paving
In the surface of conveyer belt, and the solvent in crystal slurry is heated and departs from crystal, realize the dress of crystal slurry serialization
Material and separation solvent.Conveyer belt concrete form has a variety of, but on the basis of present inventive concept is not departed from, can realize crystal
Separation solvent, drying are carried out in the state of crystal grain geo-stationary, should just belong to protection scope of the present invention.
The bottom of transmission load bearing component 210 of the present embodiment is provided with heater 310, and there are the heater 310 4 to add
Hot arc 311, described bringing-up section 311 are internally heated by medium heat-transfer or electrical heating to closed container 110, heating
Mode and form have it is a variety of, but on the basis of present inventive concept is not departed from, crystal can be realized in crystal grain heating and
The mode of heating not reacted with crystal, it should just belong to protection scope of the present invention.And transmission load bearing component 210 is by adding
Material end to discharge end, the heating-up temperature of bringing-up section 311 gradually rises, as shown in figure 1, by feed end to discharge end, 4 bringing-up sections
311 heating-up temperatures for being radiated to crystal slurry are respectively 40 ± 5 DEG C, 80 ± 5 DEG C, 120 ± 5 DEG C, 180 ± 5 DEG C.Wherein, add
Thermal medium is water and steam or thermal conductivity oil.The heating-up temperature that described bringing-up section 311 is radiated to crystal slurry is 40-
180℃.The inlet end of air extractor 120 is connected with closed container 110, and the air extractor 120 is sustainable by closed container
Gas discharge inside 110, so as to build vacuum environment in closed container 110；The outlet side of air extractor 120 and solvent are cold
Solidifying device 520 is connected, the organic solvent condensate that solvent condensing device 520 can be by crystal by thermal release, so as to which crystal be taken off
From solvent condense recovery, improve solvent the rate of recovery and recovery purity, to reduce production cost.
Depart from the blocked isocyanate preparation method of solvent under the crystal grain relative static conditions of the present invention, specific steps are such as
Under：
Step 1: synthesize and separate out crystal
1) solvent and sealer are put into reactor, then reactor is warming up to reflux dewatering, until in water knockout drum not
There is globule precipitation again；
2) reactor is cooled to 80 DEG C, and isocyanate-monomer is put into reactor, then reactor is warming up to 100
DEG C, and 1 hour is incubated, the material in reactor is cooled to normal temperature by insulation after terminating during stirring, separates out white knot
Brilliant thing, obtain crystal slurry.Wherein the addition of solvent is 1L/ isocyanate-monomer kg, i.e., often adds 1kg isocyanates lists
Body, then add 1L solvents.
Above-mentioned isocyanate-monomer is：Thick MDI, methyl diphenylene diisocyanate, TDI or its dimer, HDI, NDI
Or the mixture of IPDI one or more kinds of materials；Above-mentioned organic solvent does not react with isocyanate-monomer
Organic solvent；Described sealer is the mixture of one or more kinds of materials in lactams, phenols or oximes.
Step 2: crystal pulp separation solvent
Open air extractor 120 to be evacuated closed container 110, vacuum environment, vacuum are built in closed container 110
Spend for -0.05MPa；By crystal slurry, uniformly dress is layered on the transmission supporting part in closed container 110 to slurry adding apparatus 510
The upper surface of part 210, the dress paving thickness of crystal slurry is 15 ± 0.5mm, and the solid content of crystal slurry is 65 ± 2%；Add
Thermal 310 has 4 bringing-up sections 311, and the heating-up temperature that bringing-up section 311 is radiated to crystal slurry is 40-180 DEG C, heating
The lasting crystal on transmission load bearing component 210 of section 311 heats.
After crystal slurry dress is layered on transmission load bearing component 210 upper surface, under the drive of transmission load bearing component 210, knot
Brilliant thing slurry constantly travels forward, and bringing-up section 311 is lasting in the process heats to crystal slurry, crystal slurry
The heated disengaging crystal of solvent in material, when crystal is transported to front end by transmission load bearing component 210, solvent removal is complete, i.e.,
Crystal, which is dried, to be completed, and obtains crystallizing composition granule, and the sustainable gas by inside closed container 110 of air extractor 120 is discharged,
The outlet side of air extractor 120 is connected with solvent condensing device 520, and solvent condensing device 520 can be by the heated disengaging of crystal
Solvent is condensed, and solvent is condensed and reclaimed.At the same time, the lasting dress of follow-up crystal slurry is taped against transmission load bearing component 210
Surface, had both realized crystal continuous production, maintained the geo-stationary between crystal crystal grain again, avoided crystal dry
Crystal formation occurs during dry desolventizing to change.
Comparative example 1
With embodiment 1, difference is the substance of this comparative example：
Step 1: synthesize and separate out crystal
The addition of solvent is 6-10L/ isocyanate-monomer kg, i.e., often adds 1kg isocyanate-monomers, then add 6-
10L solvents, this comparative example use for 8L.
Step 2: fractional crystallization thing and recycling design concretely comprise the following steps：
(1) centrifugal treating is carried out to crystal slurry, separates mother liquor, slurry mother liquor and crystal under the influence of centrifugal force
Separation, wherein the solid content of crystal slurry is 20%-30%；The mother liquor being centrifugally separating to obtain need to distill again can just obtain it is pure
Net solvent；
(2) crystal after centrifuging, which is put into drying box, to be dried in vacuo, wherein vacuum drying temperature is 70 DEG C, very
Empty dried material is put into hot-air drier, and the temperature of heated-air drying is 110 DEG C, obtains crystallizing composition granule after the completion of drying.
By being contrasted to embodiment 1 and comparative example 1：
(1) original technology using centrifuge due to being separated so that the viscosity of crystal slurry can not in centrifugal process
It is too big, it is desirable to which that crystal slurry solid content is 20%-30%, and relative to the prior art of comparative example 1, present application improves viscous
The acceptable degree of degree, so as to reduce the usage amount of solvent in production process；
(2) crystal during centrifuging in solvent is not yet kept completely separate from solvent, and mother liquor distil(l) is molten
Part crystal residue can be produced during agent, so as to reduce the output yield of crystal；And the production technology of the present invention
Directly crystal slurry is thermally dried under relative static conditions and separates solvent, in heating process solvent directly by
Heat is separated with crystal, and so as to eliminate the still-process of mother liquor Extraction solvent, crystal is directly obtained after the completion of vacuum drying
Particle, improves the yield of product, and yield reaches calculated value；
(3) solvent volatilizing loss is big when centrifuging crystal slurry mother liquor, and solvent is difficult to effective recycling so that every
Ton product will consume 400-600kg solvents, and production technology of the invention, which eliminates, centrifuges mother liquor step, and in closed environment
Lower completion heating in vacuum separation solvent so that solvent is sufficiently recycled, and not only increases the rate of recovery of solvent, and
Solvent does not contact with the external world, reduces production cost, and prevents solvent contamination environment.
Prior art forms during blocked isocyanate is produced and first centrifuges mother liquor, vacuum drying again
Two-step method separation, drying steps.And the crystallization composition granule that realizes of the invention separates with a step of solvent, and save
The step of centrifugation.For the technology, ten thousand can not be simply considered that this is that conventional technique selection can be achieved with, it is contemplated that
It can be achieved with if this is conventional selection, in order to which crystallization composition granule is separated with solvent, then existing technical staff should
It is very simple just to separate crystal with solvent it is contemplated that directly heating, then this method should already turn into prior art.But
It is to be found from literature search, in the prior art often using first centrifuging mother liquor, be dried in vacuo prepare crystal again
Grain, use seem simple direct-fired method and separate both.Therefore, it is not that simple heating will can just tie
Brilliant thing efficiently separates with solvent, but insoluble technical problem be present just so that existing technical staff has to using first
Centrifugation, the mode of re-dry prepare crystallization composition granule；Importantly, existing technical staff not yet has found this before this
During technical barrier, also will not go solve the technical barrier using any technical scheme certainly.
Present application separates solvent by carrying out heating in the state of geo-stationary between crystal crystal grain is kept, from
And realize to directly heat and separate crystallization composition granule with solvent.It is both no in the prior art to disclose any document for the technology,
Do not provide any enlightenment information yet, present application breaks the technology prejudice of prior art, and improve solvent separative efficiency,
Production efficiency, reduce production cost.There is unobviousness accordingly, with respect to prior art, and with protrusion
Substantive distinguishing features and marked improvement.As for the reaction mechanism during this, applicant is also not completely clear, by multiple
Investigation thinks that this is probably because if it happens crystal disturbs during heating separates solvent, and crystal will be made brilliant
Crystal transfer occurs for grain, so as to have a strong impact on the product quality of crystal.
Embodiment 2
As shown in Fig. 2 the substance of the present embodiment, with embodiment 1, difference is：Transmit load bearing component 210
Can be the loading plate moved relative to slurry adding apparatus 510, the loading plate can be done back and forth relative to slurry adding apparatus 510
Motion, during loading plate moves back and forth, crystal slurry uniformly fills the surface for being laid on loading plate, realizes crystal in crystalline substance
Heating separation solvent is carried out in the state of grain geo-stationary, and crystal slurry drying is obtained into blocked isocyanate particle.When
So, transmission load bearing component 210 may also be the fixed plate of stationary state, now only need the charge door of slurry adding apparatus 510 relative
Moved reciprocatingly in fixed plate, crystal slurry can equally be filled and be laid on transmission load bearing component 210 surface.Transmit supporting part
The concrete form of part 210 has a variety of, but on the basis of present inventive concept is not departed from, can realize that crystal is relatively quiet in crystal grain
Separation solvent, drying are carried out in the state of only, should just belong to protection scope of the present invention.
By crystal slurry, uniformly dress is layered on the transmission in closed container 110 to the slurry adding apparatus 510 of the present embodiment
The upper surface of load bearing component 210, the dress paving thickness of crystal slurry be 2 ± 0.5mm, and the solid content of crystal slurry for 40 ±
2%.The transmission bottom of load bearing component 210 is provided with 8 bringing-up sections by feed end to discharge end, and 8 bringing-up sections 311 are radiated to crystallization
The heating-up temperature of thing slurry is respectively 40 ± 5 DEG C, 60 ± 5 DEG C, 80 ± 5 DEG C, 100 ± 5 DEG C, 120 ± 5 DEG C, 140 ± 5 DEG C, 160
±5℃、180±5℃。
Embodiment 3
Shown in Fig. 3 and Fig. 4, with embodiment 1, difference is the substance of the present embodiment：Transmit load bearing component 210
Can also be the loading plate moved relative to slurry adding apparatus 510, wherein loading plate is at least divided into two-part (such as Fig. 3 institutes
Show), by taking the loading plate of two-part as an example, it is rotatablely connected between the loading plate of two-part by hinge or rotary shaft, the carrying
Plate can move reciprocatingly relative to slurry adding apparatus 510, and during loading plate moves back and forth, crystal slurry uniformly fills
It is laid on the surface of loading plate so that crystal slurry heats separation solvent on loading plate.And transmission load bearing component 210 bottom is set
Two particle collection devices 410 are equipped with, two particle collection devices 410 are respectively positioned at the both ends end of transmission load bearing component 210
(as shown in Figure 3).The motion process of embodiment 3 is described and illustrated with reference to Fig. 4, in the process of heating separation solvent, slurry
Adding apparatus 510 adds crystal slurry in loading plate, loading plate first lateral movement to the left, during loading plate moves,
Crystal slurry uniformly fills the left part for being layered on loading plate, now right when loading plate moves to the extreme position in left side
Half side loading plate moves to the bottom of slurry adding apparatus 510, and slurry adding apparatus 510 starts crystal slurry being added to right side
Carry plate surface, treat left side loading plate crystal pulp separation solvent, dry after, put down left side loading plate, left side is held
Support plate end is connected with the entrance of particle collection device 410, separates the crystallization composition granule after solvent and is directly discharged into particle collection device
410 entrances (as shown in Figure 4)；Then loading plate starts lateral movement to the right, and the motion process on right side and left side are essentially identical, this
Embodiment it is above-mentioned be position relationship in Fig. 4 " up and down ", these position relationships are intended merely to better illustrate and retouched
The present embodiment is stated, and protection scope of the present invention is not construed as limiting.
By crystal slurry, uniformly dress is layered on the transmission in closed container 110 to the slurry adding apparatus 510 of the present embodiment
The upper surface of load bearing component 210, the dress paving thickness of crystal slurry be 8 ± 0.5mm, and the solid content of crystal slurry for 60 ±
2%.
Embodiment 4
As shown in figure 5, the isolation air element of the present invention includes closed container 110 and protective gas feeder 130, its
Middle crystal load bearing unit is arranged in closed container 110, and closed container 110 separates solvent for crystal and provides closed-loop
Border, protective gas feeder 130 supply protective gas to closed container 110 and have completely cut off air to crystal slurry drying process
Influence；Crystal load bearing unit is fixed load bearing component 220, i.e., fixed load bearing component 220 is provided with closed container 110,
Fixed load bearing component 220 is used to carrying or holding crystal, and the fixation load bearing component 220 is the accommodating disc-shaped knot of crystal slurry
Structure, or the platy structure of dress paving crystal slurry, or hold the container of crystal slurry.Protective gas feeder
130 outlet side is connected by pipeline with closed container 110, and protective gas feeder 130 is built with protective gas, protection
Gas is N2、CO2Or one or more kinds of mixtures in inert gas.Described protective gas feeder 130 with it is close
Protection gas heater block 320 is provided with the pipeline closed between container 110.
Depart from the blocked isocyanate preparation method of solvent under the crystal grain relative static conditions of the present invention, specific steps are such as
Under：
Step 1: synthesize and separate out crystal
1) solvent and sealer are put into reactor, then reactor is warming up to reflux dewatering, until in water knockout drum not
There is globule precipitation again；
2) reactor is cooled to 70 DEG C, and isocyanate-monomer is put into reactor, then reactor is warming up to 100
DEG C, and it is incubated 1 hour.Material in reactor is cooled to normal temperature by insulation after terminating during stirring, separates out white knot
Brilliant thing, obtain crystal slurry.
Step 2: crystal pulp separation solvent
By crystal slurry, uniformly dress is layered on the fixed upper surface of load bearing component 220, and the wherein addition of solvent is that 3L/ is different
Cyanate ester monomer kg, i.e., 1kg isocyanate-monomers are often added, then add 3L solvents.Crystal slurry dress paving thickness be 10 ±
0.1mm, and the solid content of crystal is 40 ± 2%；Then fixed load bearing component 220 is put into closed container 110, and kept
Fixed load bearing component 220 remains static, so as to prevent crystal slurry from relative motion occurring during drying.
Open protective gas feeder 130 and be passed through protective gas to closed container 110, gas to be protected is by closed container
, can be by checking that oxygen content checks whether closed container 110 is arranged completely in gas outlet after gas in 110 is completely exhausted out
Go out；Protection gas heater block 320 is opened, the protective gas of protective gas feeder 130 is heated to obtain high temperature protection
Gas, during protective gas enters in closed container 110, high temperature protection gas slowly need to be kept to enter, avoid producing wind
Or flow perturbation and influence the drying process of crystal slurry, wind or flow perturbation will all cause crystal in drying process
Relative motion between crystal grain, and influence crystal crystal formation and product quality.The temperature of high temperature protection gas is 40-180 DEG C, preferably
120 ± 5 DEG C, i.e., the temperature for the protective gas being subsequently passed through in closed container 110 is 120 ± 5 DEG C.High temperature protection gas enters close
After closing container 110, with the crystal slurry in fixed load bearing component 220 heat transfer occurs for high temperature protection gas, so as to crystallization
Thing slurry is heated, the solvent release crystal in heating process in crystal slurry, and solvent heating departs from the mistake of crystal
Geo-stationary between holding crystal crystal grain in journey.After the completion of solvent separation, removing, then load bearing component 220 will be fixed together with knot
Brilliant composition granule together takes out.
During crystal slurry heat drying, protective gas equally can be by solvent gas by closed container 110
Middle discharge, the gas outlet of closed container 110 are connected with solvent condensing device 520, and solvent condensing device 520 is to solvent gas and protection
Gas, which is fractionated, respectively obtains solvent and protective gas.
Embodiment 5
With embodiment 4, difference is the substance of the present embodiment, in addition to air extractor 120, that is, completely cuts off air
Unit includes closed container 110, air extractor 120 and protective gas feeder 130.During completely cutting off air, can first it beat
Air extractor 120 is driven to be evacuated closed container 110；After the completion of pumping, protective gas feeder 130 is opened to closed appearance
Device 110 is passed through protective gas, after protective gas is full of in closed container 110, protection gas heater block 320 is opened, to protection
The protective gas of gas feeder 130 is heated to obtain high temperature protection gas, enters the mistake of closed container 110 in protective gas
Cheng Zhong, high temperature protection gas slowly need to be kept to enter.The temperature of high temperature protection gas is 40-180 DEG C, is originally embodied as 50 ± 5 DEG C.
During crystal slurry heat drying, the sustainable gas by inside closed container 110 of air extractor 120
Body is extracted out, and gas therein includes solvent gas and protective gas, outlet side and the solvent condensing device 520 of air extractor 120
It is connected, solvent condensing device 520 is fractionated to solvent gas with protection gas respectively obtains solvent and protective gas.
Embodiment 6
As shown in figure 1, being provided with 2 bringing-up sections by feed end to discharge end, 2 bringing-up sections 311 are radiated to crystal slurry
The heating-up temperature of material is respectively 60 ± 5 DEG C, 160 ± 5 DEG C.
Depart from the blocked isocyanate preparation method of solvent under the crystal grain relative static conditions of the present invention, specific steps are such as
Under：
Step 1: synthesize and separate out crystal
1) solvent and sealer are put into reactor, then reactor is warming up to reflux dewatering, until in water knockout drum not
There is globule precipitation again；
2) reactor is cooled to 60 DEG C, and isocyanate-monomer is put into reactor, then reactor is warming up to 110
DEG C, and 1 hour is incubated, the material in reactor is cooled to normal temperature by insulation after terminating during stirring, separates out white knot
Brilliant thing, obtain crystal slurry.Wherein the addition of solvent is 4L/ isocyanate-monomer kg, i.e., often adds 1kg isocyanates lists
Body, then add 4L solvents.
Step 2: fractional crystallization thing and recycling design
Open air extractor 120 to be evacuated closed container 110, vacuum environment is built in closed container 110, wherein
Vacuum is -0.09MPa；Crystal slurry is uniformly filled the transmission being layered in closed container 110 and held by slurry adding apparatus 510
The upper surface of part 210 is carried, the dress paving thickness of crystal slurry is 1 ± 0.5mm, and the solid content of crystal slurry is 35 ± 2%；
Heater 310 has 2 bringing-up sections 311, and the heating-up temperature that bringing-up section 311 is radiated to crystal slurry is 60-160 DEG C, is added
The lasting crystal slurry on transmission load bearing component 210 of hot arc 311 heats, and the solvent in crystal slurry is heated de-
From crystal, when crystal is transported to front end by transmission load bearing component 210, solvent release is complete, i.e., crystal, which is dried, completes,
Obtain crystallizing composition granule.The sustainable gas by inside closed container 110 of air extractor 120 is discharged, and gas therein includes
Solvent gas, the outlet side of air extractor 120 are connected with solvent condensing device 520, solvent condensing device 520 can by crystal by
The organic solvent condensate of thermal release, recovery.
The present invention is described in detail above in conjunction with specific exemplary embodiment.It is understood, however, that it can not take off
Various modifications and variations are carried out in the case of from the scope of the present invention being defined by the following claims.Detailed description and drawings
Should be to be considered only as it is illustrative and not restrictive, if there is any such modifications and variations, then they all will
Fall into the scope of the present invention described here.In addition, background technology is intended to illustrate the Development Status of this technology and meaning,
It is not intended to limit the application field of the present invention or the application and the present invention.
More specifically, although the exemplary embodiment of the present invention has been described herein, but the invention is not limited in
These embodiments, but including those skilled in the art according to above detailed description it can be appreciated that it is modified, omit,
Any and whole embodiments of (such as between each embodiment) combination, adaptive change and/or replacement.In claim
Restriction can widely be explained according to the language used in claim, and be not limited in foregoing detailed description or in reality
The example described during this application is applied, these examples are considered as nonexcludability.It is in office where method or process claims
In any step for enumerating can in any order perform and be not limited to the order proposed in claim.Therefore, it is of the invention
Scope only should be determined by appended claims and its legal equivalents, rather than by descriptions and examples given above Lai
It is determined that.
Claims (16)
- A kind of 1. application of solvent separation equipment in blocked isocyanate crystal separates dissolving agent process, it is characterised in that：Envelope The solvent closed in isocyanates crystal slurry departs from crystal in solvent separation equipment, during solvent release crystal Geo-stationary between holding crystal crystal grain, the solvent separation equipment includeCompletely cut off air element, the isolation air element is used to completely cut off influence of the air to crystal pulp separation dissolving agent process；Crystal load bearing unit, the crystal load bearing unit are used to keep in the state of geo-stationary entering between crystal crystal grain Row heating separation solvent；Heating unit, the heating unit are used to provide thermal source for crystal pulp separation solvent.
- 2. a kind of solvent separation equipment according to claim 1 is separated in blocked isocyanate crystal in dissolving agent process Using, it is characterised in that：Crystal load bearing unit holds for transmission load bearing component (210) or fixed load bearing component (220), the transmission Carry part (210) and fixed load bearing component (220) is used to carry crystal slurry.
- 3. a kind of solvent separation equipment according to claim 2 is separated in blocked isocyanate crystal in dissolving agent process Using, it is characterised in that：Described transmission load bearing component (210) is conveyer belt, during conveyer belt moves, crystal slurry The uniform dress of material is laid on the surface of conveyer belt, and the dress of crystal slurry serialization on a moving belt spreads and heats separation solvent.
- 4. a kind of solvent separation equipment according to claim 2 is separated in blocked isocyanate crystal in dissolving agent process Using, it is characterised in that：Described transmission load bearing component (210) is reciprocating loading plate, the reciprocating mistake of loading plate Cheng Zhong, crystal slurry uniformly fill the surface for being laid on loading plate so that crystal slurry heats separation solvent on loading plate.
- 5. a kind of solvent separation equipment according to claim any one of 1-4 separates solvent in blocked isocyanate crystal During application, it is characterised in that：Isolation air element includes closed container (110) and air extractor (120), wherein crystallizing Thing load bearing unit is arranged in closed container (110), and closed container (110) provides enclosed environment for crystal slurry drying, takes out Gas in closed container (110) is extracted out and builds vacuum environment by device of air (200).
- 6. a kind of solvent separation equipment according to claim any one of 1-4 separates solvent in blocked isocyanate crystal During application, it is characterised in that：Isolation air element includes closed container (110) and protective gas feeder (130), Wherein crystal load bearing unit is arranged in closed container (110), and closed container (110) separates solvent for crystal and provides envelope Closed loop border, protective gas feeder (130) have completely cut off air to crystal slurry to closed container (110) supply protective gas The influence of drying process；Described protective gas is N2、CO2Or one or more kinds of mixtures in inert gas.
- 7. a kind of solvent separation equipment according to claim 5 is separated in blocked isocyanate crystal in dissolving agent process Using, it is characterised in that：Also includeSlurry adding apparatus (510), the slurry adding apparatus (510) are used to crystal slurry dress being laid on crystal load bearing unit Surface；Particle collection device (410), the particle collection device (410) are used to crystallize composition granule after accepting separation solvent；Solvent condensing device (520), the solvent condensing device (520), which is used to condense solvent, to be reclaimed；Described particle collection device (410) is located at the bottom of crystal load bearing unit, and particle collection device (410) is arranged at One end away from slurry adding apparatus (510)；Described heating unit is heater (310), described solvent condensing device (520) it is connected through air extractor (120) with closed container (110).
- 8. a kind of solvent separation equipment according to claim 6 is separated in blocked isocyanate crystal in dissolving agent process Using, it is characterised in that：Also includeSlurry adding apparatus (510), the slurry adding apparatus (510) are used to crystal slurry dress being laid on crystal load bearing unit Surface；Particle collection device (410), the particle collection device (410) are used to crystallize composition granule after accepting separation solvent；Solvent condensing device (520), the solvent condensing device (520), which is used to condense solvent, to be reclaimed；Described particle collection device (410) is located at the bottom of crystal load bearing unit, and particle collection device (410) is arranged at One end away from slurry adding apparatus (510)；Described heating unit is heater (310) or high-temperature gas, and described is molten Agent condensing unit (520) is connected with closed container (110).
- 9. separating the blocked isocyanate preparation method of solvent under crystal grain relative static conditions, its step is：Step 1：Solvent, sealer, isocyanate-monomer are synthesized and separate out crystal；Step 2：Crystal slurry is heated in the state of air is completely cut off, it is molten in crystal slurry in heating process Agent departs from crystal, and solvent heating keeps geo-stationary between crystal crystal grain during departing from crystal, starches crystal Material separation solvent obtains blocked isocyanate particle.
- 10. the blocked isocyanate preparation method of solvent is separated under crystal grain relative static conditions according to claim 9, its It is characterised by：By crystal slurry as being added on transmission load bearing component (210) or fixed load bearing component (220) in step 2 Thermal release solvent.
- 11. the blocked isocyanate preparation method of solvent is separated under crystal grain relative static conditions according to claim 10, It is characterized in that：Described transmission load bearing component (210) is conveyer belt, and during conveyer belt moves, crystal slurry is equal Even dress is laid on the surface of conveyer belt, and the dress of crystal slurry serialization on a moving belt spreads and heats separation solvent；Or institute The transmission load bearing component (210) stated is reciprocating loading plate, and during loading plate moves back and forth, crystal slurry is uniform Dress be laid on the surface of loading plate so that crystal slurry heats separation solvent on loading plate.
- 12. the blocked isocyanate preparation method of solvent is separated under crystal grain relative static conditions according to claim 11, It is characterized in that：The addition of solvent is 1-4L/ isocyanate-monomers kg during synthetically prepared isocyanates in step 1.
- 13. the blocked isocyanate preparation method of solvent is separated under crystal grain relative static conditions according to claim 12, It is characterized in that：The solid content of crystal slurry is 35%-65% in step 2, and the dress paving in crystal slurry heating process is thick Spend for 1-15mm.
- 14. the blocked isocyanate system of solvent is separated under the crystal grain relative static conditions according to claim any one of 9-13 Preparation Method, it is characterised in that：The state for completely cutting off air in step 2 be build in the closed container (110) vacuum environment or Protective gas is full of in closed container (110), described protective gas is N2、CO2Or the one or more in inert gas Mixture.
- 15. the blocked isocyanate system of solvent is separated under the crystal grain relative static conditions according to claim any one of 9-13 Preparation Method, it is characterised in that：Thermal source is provided for the heating of crystal slurry by heater (310) in step 2, described adds Thermal (310) has 2-8 bringing-up section (311), and the heating-up temperature that bringing-up section (311) is radiated to crystal slurry is 40-180 ℃。
- 16. the blocked isocyanate preparation method of solvent is separated under crystal grain relative static conditions according to claim 14, It is characterized in that：Thermal source is provided for the heating of crystal slurry by high-temperature gas in step 2, described high-temperature gas is high temperature Protective gas, the temperature of high-temperature gas is 40-180 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611101581.3A CN106582055B (en) | 2016-12-05 | 2016-12-05 | A kind of preparation method of application and blocked isocyanate of the solvent separation equipment in blocked isocyanate crystal separates dissolving agent process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611101581.3A CN106582055B (en) | 2016-12-05 | 2016-12-05 | A kind of preparation method of application and blocked isocyanate of the solvent separation equipment in blocked isocyanate crystal separates dissolving agent process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106582055A CN106582055A (en) | 2017-04-26 |
| CN106582055B true CN106582055B (en) | 2018-02-09 |
Family
ID=58594816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611101581.3A Active CN106582055B (en) | 2016-12-05 | 2016-12-05 | A kind of preparation method of application and blocked isocyanate of the solvent separation equipment in blocked isocyanate crystal separates dissolving agent process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106582055B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948432A (en) * | 2010-08-03 | 2011-01-19 | 河南斯维科技有限公司 | 3.5-dimethyl pyrazol closed isophorone diisocyanate monomer additive product and preparation method thereof |
| CN204563638U (en) * | 2015-01-08 | 2015-08-19 | 安徽东至广信农化有限公司 | A kind of band-type vacuum drier for the production of agricultural chemicals |
| CN105651006A (en) * | 2014-11-10 | 2016-06-08 | 陆文光 | Multifunctional environment-friendly energy-saving vacuum belt drier set and powder drying method thereof |
-
2016
- 2016-12-05 CN CN201611101581.3A patent/CN106582055B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948432A (en) * | 2010-08-03 | 2011-01-19 | 河南斯维科技有限公司 | 3.5-dimethyl pyrazol closed isophorone diisocyanate monomer additive product and preparation method thereof |
| CN105651006A (en) * | 2014-11-10 | 2016-06-08 | 陆文光 | Multifunctional environment-friendly energy-saving vacuum belt drier set and powder drying method thereof |
| CN204563638U (en) * | 2015-01-08 | 2015-08-19 | 安徽东至广信农化有限公司 | A kind of band-type vacuum drier for the production of agricultural chemicals |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106582055A (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104829495B (en) | A kind of method that two-component solvent prepares high-purity high-yield Metformin hydrochloride | |
| CN104119250A (en) | Production method of high-purity metformin hydrochloride | |
| CN107674033A (en) | A kind of nitroimidazole production technology of 2 methyl 5 | |
| CN106582055B (en) | A kind of preparation method of application and blocked isocyanate of the solvent separation equipment in blocked isocyanate crystal separates dissolving agent process | |
| CN101367796B (en) | Process for preparing triglycidyl isocyanurate | |
| CN105732327B (en) | A kind of microwave reaction prepares the method and device of antimony glycol | |
| CN109573967A (en) | A kind of preparation method of hydroxylamine hydrochloride | |
| CN206228974U (en) | A kind of solvent separation equipment for blocked isocyanate crystal | |
| CN103102507A (en) | Preparation method of rubber antioxidant DTPD (N,N'-Bis(methylphenyl)-1,4-benzenediamine) | |
| CN111747868B (en) | Preparation method of p-phenylene diisocyanate | |
| CN101790510A (en) | Method for the production of isocyanates | |
| CN102675640B (en) | Method for controlling process conditions for production and synthesis of polyphenylene sulfide | |
| CN110054570A (en) | A kind of recovery method of 1098 by-product of antioxidant | |
| CN112110872B (en) | Cephalosporin active ester intermediate and continuous preparation method thereof | |
| US2757185A (en) | Substituted di (isocyanatophenyl) ureas | |
| CN106496215B (en) | High-yield green environment-friendly synthetic method of thiamethoxam | |
| CN101434597A (en) | Method for recycling imidacloprid from imidacloprid production mother liquor | |
| CN104447675B (en) | A kind of production technology of R propene carbonates | |
| WO2009152541A1 (en) | Method and array for pretreating polymer materials | |
| CN101691392A (en) | Method for preparing 3beta-acetoxyl group-5androstene-17ketone | |
| CN101948482A (en) | Process for producing glyphosate ammonium dry powder | |
| JPS61136523A (en) | Production of polyarylene sulfide | |
| CN102746238A (en) | Preparation method of pyrimethanil | |
| CN102267706A (en) | Method for preparing potassium nitrate | |
| CN109535113A (en) | A kind of maltol lyophilization method and device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |