CN105601999A - Antioxidant 168 in shape of bead-shaped particles and preparation method and application thereof - Google Patents

Antioxidant 168 in shape of bead-shaped particles and preparation method and application thereof Download PDF

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Publication number
CN105601999A
CN105601999A CN201610032061.5A CN201610032061A CN105601999A CN 105601999 A CN105601999 A CN 105601999A CN 201610032061 A CN201610032061 A CN 201610032061A CN 105601999 A CN105601999 A CN 105601999A
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antioxidant
pump
tower
falling film
film evaporator
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CN105601999B (en
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佟立新
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides an antioxidant 168 in the shape of bead-shaped particles and a preparation method and application thereof. The particle size of the antioxidant 168 in the shape of bead-shaped particles is 10-160 meshes. The method comprises the step of preparing molten granulating raw materials into the antioxidant 168 in the shape of bead-shaped particles by using a spraying granulating system through a granulating procedure. The granulating system comprises an insulating pump, a spraying granulating tower, an induced draft fan and an airlock; a spraying head which is connected with the insulating pump and sprays downwards is arranged on the top of the tower, and a jacket is arranged on the periphery of the spraying head; an air inlet and an air outlet are respectively formed in positions, which are close to the bottom end and the top end, of the tower; the induced draft fan is connected with the air outlet through a pipeline; and the airlock is arranged at the bottom end of the tower. By the antioxidant 168 in the shape of bead-shaped particles, the problems that a powdery antioxidant 168 is difficult to charge and meter and blockage and wall hanging are caused are solved; and the antioxidant 168 in the shape of bead-shaped particles is large in bulk density, low in volatility and convenient to package, convey and store, storage cost is reduced, 'fish eyes' and air bubbles cannot be formed on plastics in a forming process, and the quality of the plastics is improved.

Description

Antioxidant 168 of bead shaped particle shape and preparation method thereof and application
Technical field
The present invention relates to antioxidant 168 and preparation method thereof and application, relate in particular to the antioxidant of bead shaped particle shape168 and preparation method thereof with application.
Background technology
Industry antioxidant 168 (antioxidant) is GW-540 class auxiliary antioxidant, with phenols main anti-oxidant1010,1076 etc. have good cooperative effect, are applicable to as polyethylene, polypropylene, polystyrene, ABS treeThe auxiliary antioxidant of fat and various fibre resins etc., has good auxiliary antioxygenic property, is phosphite esterClassic kind in class auxiliary antioxidant. But the antioxidant 168 that prior art provides is all white crystalsPowder, this white crystalline powder easily causes dust pollution, and exists and cause adding because of its poor fluidity in applicationMaterial and metering wall built-up, the phenomenon of unfavorable process control such as " crane span structures ", and then easily cause obstruction, the unequal impact product of batch mixingThe technical problem of product quality.
Prior art conventionally adopts following two kinds of methods to carry out granulating to powdery product, and to solve, powder-product bringsTechnical problem:
(1) extrinsion pressing, is limited in specific space by powder material, compresses as close by applying external forceReal state, the success or not of extrusion modling, depends on effective utilization and the transmission of externally applied forces, the opposing party on the one handFace depends on the physical property of granule materials. Its equipment mainly contains single dual-screw pelletizer, to roller gear comminutor, postPlug extruder etc. Without any change, in extrusion modling process, there is secondary in the production link feature of environmental protection in this methodPollution problem, is being used link contaminative to make moderate progress, but not thorough, the product particle of producing by the method is strongSpend lower, easily broken in packaging, transport, storing process, still there is a small amount of dust, at production link andUse link potential safety hazard still to exist.
(2) hot melt molding method, it is to utilize the low melting point characteristic of product that the material of melting is passed through to special condensing mode,Make its condensation-crystallization become needed sheet, strip, bulk and the shape such as hemispherical. Its equipment mainly contains rotary drum knot sheetMachine and the revolution cold belt film forming machine that falls. No matter the advantage of the method maximum is at production link or is using link allSolved environmental issue, but this technique has significant limitation, product fusing point must be lower, the product under molten conditionProduct viscosity must be less, and flat, the particle of product of producing by the method is large, poor fluidity, and this just causes product to existWhen use, the accuracy of convenience, free-running property, metering and controllability reduce greatly. For antioxidant 168, it is moltenO'clock up to 180 DEG C, and its viscosity is large especially after fusing, and those skilled in the art are difficult to adopt hot melt molding methodPowdered antioxidant 168 is prepared into graininess antioxidant.
Therefore, how granulating antioxidant 168 with overcome its technical problem of bringing be those skilled in the art urgentlyThe technical problem solving.
Summary of the invention
One of object of the present invention is to provide a kind of antioxidant 168 of bead shaped particle shape, this bead shaped particle shape anti-Oxidant 168 granularities are large, bulk density is large, volatility is low.
Another object of the present invention is to the preparation method of the antioxidant 168 of the bead shaped particle shape that provides described, the partyMethod can be effectively by antioxidant 168 bead shaped particle shapes.
A further object of the present invention is the application of the antioxidant 168 that described bead shaped particle shape is provided.
For achieving the above object, on the one hand, the invention provides a kind of antioxidant 168 of bead shaped particle shape, wherein,The granularity of the antioxidant 168 of this bead shaped particle shape is 10～160 orders; Preferably, described bead shaped particle shape is anti-oxidantThe granularity of agent 168 is 18～100 orders, and bulk density is 0.4～0.7g/cm3; More preferably, described antioxidant 168Heating loss≤0.2%, and/or angle of repose≤25 °.
The granularity of the antioxidant 168 of bead shaped particle shape provided by the invention is far longer than anti-oxidant that prior art providesAgent 168, has not only avoided dust pollution or blast, and has overcome the reinforced of conventional Powdered antioxidant 168With the shortcoming such as metering difficulty and obstruction, wall built-up, and then production efficiency and the quality of Plastic Rubber Products are improved. In addition,Its bulk density is large, and volatility is low, is convenient to packaging, transports and deposit, and makes to store cost and greatly reduces. Due to volatilityStep-down, makes plastic product in forming process, be unlikely to form " flake " and bubble, has greatly improved plastic productsQuality.
In the present invention, antioxidant 168 principal components refer to tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester. Remove the present invention specialOutside explanation, antioxidant 168 of the present invention is except appearance index is bead shaped particle shape, and other indexs meet correspondingProfessional standard, for example professional standard HG/T-3712-2010.
On the other hand, the invention provides a kind of preparation method of antioxidant 168 of described bead shaped particle shape, the methodComprise: adopt sprinkling pelleting system, by granulating working procedure, molten state antioxidant 168 granulating raw materials are made to described pearl shapeGranular antioxidant 168;
Described sprinkling pelleting system comprises thermal insulation pump, sprinkling pelleting tower, air-introduced machine and Blowing stopper, described sprinkling pelleting towerThe tower top setting spray head spraying downwards that is connected with thermal insulation pump, this spray head periphery arranges chuck; Described sprinkling pelleting towerNear bottom and top, air inlet and air outlet are set respectively; Described air-introduced machine is connected with described air outlet by pipeline;Described Blowing stopper is arranged at sprinkling pelleting tower bottom;
Preferably, described sprinkling pelleting system also comprises cyclone separator, sack cleaner and heat exchanger, described air-outMouth is connected with described cyclone separator, described sack cleaner, described air-introduced machine and described heat exchanger successively by pipeline;The gas vent of described heat exchanger is connected with described air inlet by air inlet pipeline;
Described granulating working procedure comprises:
Start described air-introduced machine, from described air inlet by sprinkling pelleting tower described in inert gas suction, in described chuckPass into heat transfer medium and heat described spray head, by described thermal insulation pump by described molten state antioxidant 168 granulating raw materialsSqueeze into described sprinkling pelleting tower and carry out sprinkling pelleting, make the antioxidant 168 of described bead shaped particle shape;
Preferably, the inert gas of extracting out from air outlet successively through described cyclone separator, sack cleaner, air-introduced machine,Heat exchanger enters sprinkling pelleting tower by described air inlet circulation.
Sprinkling pelleting system of the present invention also can be provided with at the gas vent of heat exchanger to the connecting line of air inletWind-warm syndrome survey meter and automatic makeup inert gas installation, be provided with tower and press survey meter and tower to press control valve in the bottom of tower.
Inert gas of the present invention includes but not limited to nitrogen (N2), helium (He), neon (Ne), argon (Ar), krypton(Kr) etc., preferred nitrogen.
In granulating working procedure of the present invention, molten state antioxidant 168 granulating raw materials spray out tiny downwards by spray headDrop, thread shape liquid is in the time declining and be subject to air-introduced machine to deliver to the inert gas flow of the rising in sprinkling pelleting tower, exampleAs stream of nitrogen gas contact, be stripped from into fine drop, fall in process and be cooled to the anti-of bead shaped particle shape by inert gasOxidant 168. The antioxidant 168 of the bead shaped particle shape being prepared by the inventive method, does not produce dust pollution,Its volatility is low, good fluidity, wall built-up while efficiently solving the reinforced and metering of antioxidant 168, and " crane span structure " causes stifledPlug, the unequal technical problem that affects product quality of batch mixing.
The present invention can pass into heat transfer medium in the sleeve pipe of spray head periphery setting, for example conduction oil, and heating spray head,Make the viscosity of molten state antioxidant 168 granulating raw materials that spray from spray head low, the antioxygen of this low viscosity molten stateAgent 168 is easily stripped from into fine drop, thereby can make the antioxidant 168 of bead shaped particle shape.
Sprinkling pelleting system of the present invention can also comprise for insulation in the middle of temporary molten state antioxidant 168Tank, this centre heat insulation tank regulates pump to be connected by pipeline and insulation.
According to specific embodiment of the invention scheme, in the method for the invention, the aperture of described spray head is 0.1～1Mm; The height of described sprinkling pelleting tower is 10～30m;
Start described air-introduced machine, the wind speed of controlling in described sprinkling pelleting tower is 0.1～1m/s; And control enters described sprayThe temperature of drenching the inert gas in granulation tower is 10～20 DEG C;
In described chuck, pass into heat transfer medium and heat described spray head, control the molten state antioxidant 168 spraying outThe temperature of granulating raw material is 210～250 DEG C;
The operating pressure of controlling described thermal insulation pump is 0.2～0.8MPa.
Particularly, in described chuck, pass into heat transfer medium heating spray head, make subsequently by the melting of this spray headThe antioxidant 168 granulating raw material temperature of state reach 210～250 DEG C; Start air-introduced machine, make the wind speed in sprinkling pelleting towerBe 0.1～1m/s, the temperature that control enters the inert gas in described sprinkling pelleting tower is 10～20 DEG C, starts thermal insulation pump,Controlling its operating pressure is 0.2～0.8MPa, the antioxidant of molten state 168 granulating raw materials is squeezed into the spray head of tower topIn, antioxidant 168 granulating raw materials of molten state spray out tiny liquid stream downwards by spray head, and thread shape liquid existsWhen decline, contact with the inert gas flow that is subject to air-introduced machine to deliver to the rising in granulation tower, be stripped from into fine drop, fallIn lower process, be cooled to by inert gas the antioxidant 168 that pearl shape is granular, fall within granulation tower bottom; Start Blowing stopper,The antioxidant 168 of bead shaped particle shape at the bottom of tower is discharged. This method is to carry out in atmosphere of inert gases, the heat of generationAmount can be shifted out by heat exchanger, and inert gas can reenter granulation tower and recycle after dedusting is cooling. The present invention adoptsAs above technological parameter can be controlled the granularity of the antioxidant 168 of the bead shaped particle shape being made by granulating working procedure of the present invention and is18～100 orders, bulk density is 0.4～0.7g/cm3, 20～25 °, angle of repose, compared to granularity and bulk density not in this scopeThe antioxidant 168 of interior bead shaped particle shape, does not more produce dust pollution by above technique gained antioxidant 168,Volatility is lower, mobility is better, wall built-up while efficiently solving the reinforced and metering of antioxidant 168, and " crane span structure " causesObstruction, the unequal technical problem that affects product quality of batch mixing.
Especially, heating loss≤0.2% of antioxidant 168 granulating raw materials of the present invention;
Preferably, these antioxidant 168 granulating raw materials are to be steamed except the tertiary fourth of 2,4-bis-by molten state antioxidant 168 crude productsBase phenol obtains; More preferably, main content >=90% of these antioxidant 168 crude products, 2,4-DTBP containsAmount≤10%. Main content >=95% of further preferred these antioxidant 168 crude products, 2,4-DTBP content≤5％。
Except being particularly limited, " heating loss (volatile matter) ", " acid number ", " melting range " in the present invention, " main content ",Definition and the method for testing phase of the definition of terms such as " 2,4-DTBP content " and method of testing thereof and professional standardWith.
According to specific embodiment of the invention scheme, in the methods of the invention, adopt the first piece-rate system to steam except 2,4-, bis-unclesButylphenol; Described the first piece-rate system comprises the first reboiler, the first falling film evaporator, the first rectifying column, firstCirculating pump and the first vavuum pump; The bottom of the bottom of described the first falling film evaporator and the first rectifying column is separately positioned on instituteState the first reboiler top and be attached thereto respectively logical; The end of the import of described the first circulating pump and described the first reboilerPortion's outlet is connected by pipeline, and the top entrance of described the first circulation delivery side of pump and described the first falling film evaporator is logicalCrossing pipeline is connected; Described the first vavuum pump is connected with described the first rectifying column tower top;
Preferably, adopt described the first piece-rate system to steam except 2,4-DTBP by refining step, described refiningOperation comprises the steps:
(1) open described vavuum pump, reduce the pressure of described the first piece-rate system, and raise described the first reboiler withThe temperature of described the first falling film evaporator;
(2) by product pump, described molten state antioxidant 168 crude products being delivered to described the first falling film evaporator carries outEvaporation, utilizes described the first circulating pump and described the first falling film evaporator to carry out circulating and evaporating, and utilizes described the first essenceHeat up in a steamer tower separation and obtain described antioxidant 168 granulating raw materials and 2,4-DTBP;
More preferably, in step (1), open described the first vavuum pump, by described the first piece-rate system pressure decreasedTo being less than or equal to 5mmHg, and the temperature of described the first reboiler and described the first falling film evaporator is increased to respectively200～250℃。
Normally, the antioxidant 168 that meets professional standard obtains through crystallization or recrystallization, recrystallization mainObject is to remove 2,4-DTBP, and crystallization or recrystallization generally need washing, centrifugation, the operation such as dry,Therefore, adopt the process for purification of recrystallization not only to need various equipment but also need to consume a large amount of organic solvents, thisAspect has increased energy consumption, also easily causes air pollution simultaneously. In addition, in the mother liquor after recrystallization, being also dissolved with part resistsOxidant 168, because impurity in mother liquor is a lot, is difficult to adopt effective method that this part antioxidant 168 is separatedOut. And direct steaming of the present invention both simplified process route except 2,4-DTBP, save again large number quipments throwingMoney, whole technical process completes under sealing condition simultaneously, greatly reduces the energy and supplies consumption, has effectively improvedThe operating mode of producing reduces environmental pollution, and starting monomer 2,4-DTBP can fully reclaim, recycle,Production cost significantly reduces. In addition, adopt piece-rate system to steam except resisting that 2,4-DTBP refining step obtainsThe heating loss of oxidant 168 is lower, and this adopts existing crystallization or recrystallizing technology to obtain. By thisHeating loss≤0.2% of the antioxidant 168 that bright refining step obtains; Even can be less.
The present invention's the first reboiler, the first falling film evaporator and the first rectifying column have formed first point of the first piece-rate systemFrom device, this first separator is collection flash distillation, falling film evaporation and the three-in-one separator of rectifying. The present invention passes through product pumpMolten state antioxidant 168 crude products are delivered to the first falling film evaporator in negative pressure state by pressurization, makes molten stateThe state of antioxidant 168 crude products become negative pressure (principle is identical with flash principle) by malleation sudden transition, wherein2,4-DTBP instant vaporization and separating. The present invention studies and finds that antioxidant 168 is in high temperature, high vacuumUnder state, easily distil or be carried, adopting this first separator can effectively stop in the time of de-2,4-DTBP,The problem that antioxidant 168 distils and/or is carried makes the 2,4-DTBP reclaiming directly utilize simultaneously.
According to specific embodiment of the invention scheme, as above in step (1), open described the first vavuum pump in the present invention,Described the first piece-rate system pressure decreased to pressure is less than or equal to 5mmHg, and by described the first reboiler with described inThe temperature of the first falling film evaporator is increased to respectively 200～250. Controlling as above process conditions can more effectively steam and remove2,4-DTBP, circulation distillation 1～3h can reach the object of steaming except 2,4-DTBP.
Particularly, the temperature of the first reboiler and the first falling film evaporator is increased to 200～250 DEG C, adopts firstVavuum pump vacuumizes, in the time that pressure is less than or equal to 5mmHg, by product pump by thick the antioxidant of molten state 168Product are delivered to the first falling film evaporator and evaporate, stop material loading in the time that the liquid level of the first reboiler reaches certain liquid level time,Adopt the first circulating pump and the first falling film evaporator to carry out circulating and evaporating to material. Now, 2 of vaporization, 4-di-t-butylPhenol and distillation or antioxidant 168 principal components that are carried separate in rectifying column, and antioxidant 168 principal components existRectifying column internal reflux is to reboiler, and isolated 2,4-DTBP steam can pass through condenser, condensationBecome liquids recovery utilization. Circulation distillation time is generally 1～3h, and sample examination for example, from pump entry sampling, is treatedChemical examination meets after standard, and the antioxidant of having purified 168 granulating raw materials are delivered to the direct granulation of granulating working procedure with circulating pumpOr in the middle heat insulation tank arranging, in order to granulation.
According to specific embodiment of the invention scheme, in method of the present invention, described antioxidant 168 crude products areMade by 2,4-DTBP and phosphorus trichloride synthetic method containing the reactant of antioxidant 168 principal components through after locateReason obtains, and described post processing comprises first stage and second stage:
The described first stage is included in and in described reactant, adds cosolvent solubilizing reaction thing, and filter, wash,Add organic base and dehydration to obtain the process containing the mother liquor of antioxidant 168 principal components;
Described cosolvent be can make described reactants dissolved and can with the solvent of water azeotropic, preferably toluene and/or dimethylbenzene;
Described second stage is the solvent steaming except in described mother liquor.
The present invention has added organic base especially compared to the post-processing operation of prior art purifying antioxidant 168, itsCan prevent on the one hand the 168 principal components hydrolysis of product antioxidant, on the other hand can with react in generation an ester orDiester generates the easy filtrate of slightly solubility, makes follow-up being difficult to be filtered and be removed by the impurity of distillation. If do not add organicAlkali, in the follow-up water smoking, antioxidant 168 principal components will be hydrolyzed and change 2,4-DTBP into.
The reactant containing antioxidant 168 principal components being made by 2,4-DTBP and phosphorus trichloride synthetic method canUndertaken by state of the art.
Preferably, after the first stage of the present invention is included in and adds cosolvent solubilizing reaction thing in described reactant,Filter for the first time successively, inorganic base washing, add organic base, dehydration and filter for the second time, obtain described mother liquor;
Preferably, adding organic base to make system pH is 7.5～11; More preferably, described organic base comprise n-butylamine,One or more in triethanolamine and triethylamine.
Preferably, described in, adding cosolvent solubilizing reaction thing is to carry out at 60～85 DEG C.
Preferably, described inorganic base washing is to carry out at 60～85 DEG C. It is 2～10% that described inorganic base can be mass fractionSig water, for example sodium hydroxide solution, potassium hydroxide solution, sodium carbonate liquor, sodium bicarbonate solution, sodium acid carbonateSolution and potassium bicarbonate solution;
Preferably, adding organic base, is to stir at 60～85 DEG C in temperature, is within 7.5～11 o'clock, to start to rise until system pHTemperature dehydration.
Preferably, when temperature to be drained off reaches 115～150 DEG C, carry out circulating filtration for the second time.
According to specific embodiment of the invention scheme, in post processing of the present invention, second stage adopts the second segregative lineSystem steams except the solvent in described mother liquor;
Wherein, described the second piece-rate system comprises the second reboiler, the second falling film evaporator, Second distillation column, secondCirculating pump; The bottom of described the second falling film evaporator and the bottom of Second distillation column are separately positioned on described the second reboilerTop is also attached thereto respectively logical; The outlet at bottom of the import of described the second circulating pump and described the second reboiler is by pipeRoad is connected, and described the second circulation delivery side of pump is connected by pipeline with the top entrance of described the second falling film evaporator;
Optionally, described the second piece-rate system also comprises the second vavuum pump, described the second vavuum pump and described the second rectifyingThe tower top of tower is connected;
Preferably, adopt the second piece-rate system to steam except the solvent in described mother liquor by desolvation operation, described in removeSolvent operation comprises the steps:
(A) the raise temperature of described the second reboiler and described the second falling film evaporator;
(B) described mother liquor is evaporated by described the second falling film evaporator, utilize described the second circulating pump and instituteState the second falling film evaporator described mother liquor is carried out to circulating and evaporating, and it is described anti-to utilize described Second distillation column separation to obtainSolvent in oxidant 168 crude products and mother liquor;
Optionally, in the time that described the second piece-rate system comprises described the second vavuum pump, described desolvation operation also comprisesStep (C);
(C) open described the second vavuum pump, reduce the pressure of described the second piece-rate system, identical by step (B)The further desolvation of mode.
The second reboiler of the present invention, the second falling film evaporator and Second distillation column have formed of the second piece-rate systemTwo separators, this separator is collection flash distillation, falling film evaporation, the separator that rectifying is three-in-one. The present invention studies discovery and works asWhen solvent vaporization, it can carry a small amount of 2,4-DTBP and antioxidant 168 principal components, adopts this pointCan effectively stop when the desolvation from device, what 2,4-DTBP and antioxidant 168 principal components were carried asksTopic makes recovered solvent directly utilize simultaneously.
According to specific embodiment of the invention scheme, in step (A), described the second reboiler and described second is fallenThe temperature of film evaporator rises to respectively 200～250 DEG C;
In step (B), described mother liquor is evaporated continuously to charging rate by described the second falling film evaporatorBe 1～3m3/h；
Optionally, in the time that described desolvation operation comprises step (C), open described the second vavuum pump, described in inciting somebody to actionThe pressure decreased of the second piece-rate system to vacuum is 0～-0.08MPa. Controlling as above process conditions can steam more effectivelyExcept the solvent in mother liquor.
Particularly, the second separator is preheating to 200～250 DEG C with conduction oil, then will be containing anti-oxidant with dnockout pumpAgent 168 principal component mother liquors evaporate by the second falling film evaporator with certain speed, be isolated into solvent gas phase andThe antioxidant 168 principal component liquid phases that comprise 2,4-DTBP, due in separating at high temperature process, solvent steamsIn vapour, can carry a small amount of 2,4-DTBP and antioxidant 168 principal components, it enters by Second distillation columnOne step is purified and is obtained the solvent vapo(u)r of higher degree, and this solvent vapo(u)r can pass through condenser, and condensation becomes liquid-circulating to be madeWith, in the second reboiler, reach certain liquid when isolating molten state antioxidant 168 crude products that contain a small amount of solvent, stop material loading when the position, open the second circulating pump, circulating and evaporating approximately 0.5～1.5 hour, can start the second vavuum pump, makesThe vacuum of the second piece-rate system is 0～-0.08MPa, further deviates from trace in anti-oxidant 168 crude products of molten state moltenAgent, sample examination, for example, from pump entry sampling, meet after standard until chemical examination, by the antioxidant of having purified 168Crude product is delivered in the direct middle heat insulation tank of refining or arrange of refining step, in order to refining with circulating pump.
Preferentially, the present invention can prepare the anti-oxidant of bead shaped particle shape of the present invention by following operation successivelyAgent 168:
(I) make molten state antioxidant 168 crude products by postprocessing working procedures of the present invention;
(II) step (I) gained molten state antioxidant 168 crude products are obtained to described melting by described refining stepState antioxidant 168 granulating raw materials;
(III) gained molten state antioxidant 168 granulating raw materials in step (II) are made by described granulating working procedureThe antioxidant 168 of described bead shaped particle shape.
Again on the one hand, the antioxidant 168 that the invention provides described bead shaped particle shape is adding as auxiliary antioxidantBe added to the application in plastics.
Using the antioxidant of bead shaped particle shape of the present invention 168 as polyethylene, polypropylene, polystyrene, ABSThe auxiliary antioxidant of resin and various fibre resins etc., with other main anti-oxidant synergies, shows excellentGood auxiliary antioxygenic property. The granularity of the antioxidant 168 of bead shaped particle shape provided by the invention is far longer than existingThe antioxidant 168 that technology provides, this has not only been avoided dust pollution or blast, and has overcome conventional PowderedThe shortcoming such as the reinforced and metering difficulty of antioxidant 168 and obstruction, wall built-up, and then the life that has improved Plastic Rubber ProductsProduce efficiency and quality. In addition, its bulk density is large, and volatility step-down is convenient to packaging, is transported and deposit, and makes to store intoThis reduces greatly. Due to volatility step-down, make plastic product in forming process, be unlikely to form " flake " and bubble,Greatly improve the quality of plastic products.
Brief description of the drawings
Fig. 1 is the process chart that embodiment 1～5 prepares bead shaped particle antioxidant 168;
The structural representation that Fig. 2 is the second piece-rate system of using in embodiment 1～5 desolvation operation; Figure acceptance of the bidNumber there is following meaning:
21: the second separators; 211: the second reboilers; 212: the second falling film evaporators; 213: Second distillation column;22: the second circulating pumps; 23: the second condensers; 24: surge tank; 25: solvent receiving tank; 26: the second vavuum pumps;
The structural representation that Fig. 3 is the first piece-rate system of using in embodiment 1～5 refining step; Number in the figure toolThere is following meaning:
31: the first separators; 311: the first reboilers; 312: the first falling film evaporators; 313: the first rectifying columns;32: the first circulating pumps; 33: the first condensers; 34:2,4-DI-tert-butylphenol compounds receiving tank;
The structural representation that Fig. 4 is the granulating system that uses in embodiment 1～5 granulating working procedure; Number in the figure have asLower meaning:
41: middle heat insulation tank; 42: insulation regulates pump; 43: sprinkling pelleting tower; 431: spray head: 432: air intakeMouthful; 433: air outlet; 434: tower is pressed control valve; 435: tower is pressed survey meter; 44: Blowing stopper; 45: cyclone dust removalDevice; 46: sack cleaner; 47: air-introduced machine; 48: circulation heat exchanger; 49:5 DEG C of water-to-water heat exchanger; 491: automaticallyMend the nitrogen inlet of nitrogen device; 492: wind-warm syndrome survey meter.
Detailed description of the invention
Understand for technical characterictic of the present invention, object and beneficial effect being had more clearly, existing to skill of the present inventionArt scheme and accompanying drawing carry out following detailed description, but can not be interpreted as restriction that can practical range of the present invention. FollowingExperimental technique described in embodiment, if no special instructions, is conventional method; Described reagent and material, as without specialIllustrate, all can obtain from commercial channels.
The first falling film evaporator using in embodiment 1～5 has following parameter:
Heat transfer medium is conduction oil; Its temperature is 300; Heat transfer area is 80m2; Operating pressure is 0.4MPa; HighDegree is 8m; Diameter is 500mm;
The second falling film evaporator using in embodiment 1～5 has following parameter:
Heat transfer medium conduction oil; Its temperature is about 300; Heat transfer area is 50m2; Operating pressure is 0.4MPa;Be highly 6m, diameter is 500mm;
The first rectifying column using in embodiment 1～5 has following parameter:
Height 10m; Diameter 800mm; 22 of the numbers of plates;
The Second distillation column using in embodiment 1～5 has following parameter:
Height 12m; Diameter 800mm; 25 of the numbers of plates;
The first reboiler using in embodiment 1～5 has following parameter:
Diameter 2200mm; Height 2.3m; Heat transfer medium conduction oil; Its temperature approximately
The second reboiler using in embodiment 1～5 has following performance parameter:
Diameter 2200mm; Height 2.5m; Heat transfer medium conduction oil; Its temperature approximately
Title and the specification of the each parts in embodiment 1～5 in sprinkling pelleting system are as shown in table 1:
Table 1
Fig. 1 is the preparation method's of the antioxidant 168 of bead shaped particle shape in embodiment 1～5 flow chart, this flow process bagDraw together and in reactant, add cosolvent, carry out circulating filtration for the first time and form pending mother liquor, then adopt inorganic base to enterRow neutralization washing, adds organic base after washing, dewater subsequently, carries out circulating filtration for the second time, then after dehydrationCarry out desolvation operation, gained solvent is recyclable to be utilized to reaction, obtains the anti-of molten state through desolvation operationOxidant 168 crude products, carry out refining step subsequently to make antioxidant 168 granulating raw materials of molten state, refining workIn order, gained 2,4-DTBP is recyclable utilizes to reaction, finally by the antioxidant of gained molten state 168Granulating raw material is prepared the antioxidant 168 of bead shaped particle shape by granulating working procedure.
Embodiment 1
In 3000L confined reaction, add the 2,4-DTBP of 1110Kg, the phosphorus trichloride, 270 of 251KgAfter the toluene solvant of L and the pyridine of 4.5Kg, at 50 DEG C of insulation reaction 1.5h, in 2 hours, be warming up to 120 DEG C,Then at 120～130 DEG C of insulation reaction 2.5h, steam except reaction dissolvent toluene, stop stirring, then in reactor againAdd 1.4m3Toluene, starts and stirs, and makes reactants dissolved, then obtains through circulating filtration for the first time at 60～85 DEG CTo the pending mother liquor of 2000L, add the sodium hydrate aqueous solution of 400Kg5%, at 60 DEG C, stir 15 minutes, quietOnly buck was separated in 15 minutes, then added the n-butylamine of 15Kg, at 60 DEG C, stir temperature 15 minutesRise to 70 DEG C, treat that pH is 8～9, the dehydration that heats up, carries out circulating filtration for the second time and must contain when still Wen Wendu reaches 120 DEG CThe mother liquor of antioxidant 168 principal components; This mother liquor evaporate to dryness to constant weight sampling is pressed to the method in HG/T3712-2010Record: 2,4-DTBP content is 4.5%.
Above-mentioned gained is carried out to desolvation operation containing the mother liquor of antioxidant 168 principal components, and this desolvation operation makesBy the second piece-rate system as shown in Figure 2, described the second piece-rate system comprises by the second reboiler 211, the second falling liquid filmThe second separator 21, the second circulating pump 22 and the second vavuum pump 26 that evaporimeter 212 and Second distillation column 213 form;The bottom of the bottom of described the second falling film evaporator 212 and Second distillation column 213 is arranged on described the second reboiler 211Top is also attached thereto respectively logical; The outlet at bottom of the import of described the second circulating pump 22 and described the second reboiler 211Be connected by pipeline, the top entrance of the outlet of described the second circulating pump 22 and described the second falling film evaporator 212 is logicalCrossing pipeline is connected; Described the second vavuum pump 26 is connected with the tower top of described Second distillation column 213; The second vavuum pump26 and Second distillation column 213 between the second condenser 23, surge tank 24 and the solvent receiving tank that are connected successively are also set25。
Described desolvation operation comprises the steps:
The second reboiler 211 and the second falling film evaporator 212 use conduction oils are preheating to 240 DEG C, and employing dnockout pump willGained contains the mother liquor of antioxidant 168 principal components with 1.5m3The speed of/h is steamed by the second falling film evaporator 212Send out, the liquid phase of antioxidant 168 principal components of isolating solvent gas phase and comprising 2,4-DTBP, carries few2 of amount, the solvent vapo(u)r of 4-di-tert-butylphenol and antioxidant 168 principal components is further carried by Second distillation column 213Purely obtain highly purified solvent vapo(u)r, this solvent vapo(u)r becomes liquid-circulating by condenser 23 condensations and uses, and works as separationWhen antioxidant 168 crude products that go out to contain the molten state of a small amount of solvent reach certain liquid level in the second reboiler 212,Stop material loading, open the second circulating pump 22, circulating and evaporating approximately 0.5～1.5 hour, then starts the second vavuum pump 26,The vacuum that makes the second piece-rate system is-0.02～-0.04MPa, further deviates from after trace solvent to obtain the antioxygen of molten stateAgent 168 crude products, antioxidant 168 crude products of this molten state, record by the method in HG/T3712-2010:Light transmittance under 425nm is 98.7%, and the transmitance under 500nm is 99.0%; Main content is 97.2%; 2,4-DI-tert-butylphenol compounds content is 1.57%.
The antioxidant of above-mentioned gained molten state 168 crude products are carried out to refining step, and this refining step uses as Fig. 3 instituteThe first piece-rate system of showing, described the first piece-rate system comprises by the first reboiler 311, the first falling film evaporator 312And first rectifying column 313 the first separator 31, the first circulating pump 32 and the first vavuum pump (not shown) that form;The bottom of the bottom of described the first falling film evaporator 312 and the first rectifying column 313 is arranged on described the first reboiler 311Top is also attached thereto respectively logical; The outlet at bottom of the import of described the first circulating pump 32 and described the first reboiler 311Be connected by pipeline, the top entrance of the outlet of described the first circulating pump 32 and described the first falling film evaporator 312 is logicalCrossing pipeline is connected; Described the first vavuum pump is connected with the tower top of described the first rectifying column 313; The first vavuum pump withThe first condenser 33 and the 2,4-DTBP receiving tank 34 that connect successively are also set between the first rectifying column 313.
Described refining step comprises the steps:
Described the first reboiler 311 is increased to 220 DEG C with the temperature of described the first falling film evaporator 312, adopts trueEmpty pump vacuumizes, and in the time that pressure is less than 3mmHg, adopts first to follow the antioxidant of gained molten state 168 crude productsRing pump 32, evaporates by the first falling film evaporator 312, in the time that the liquid level of the first reboiler 313 reaches certain liquid level, stopsWhile stopping material loading, adopt the first circulating pump 32 and the first falling film evaporator 312 to carry out circulating and evaporating to material. Now, vapourThe 2,4-DTBP of changing and antioxidant 168 principal components of distillation separate in the first rectifying column 313, antioxygenAgent 168 principal components are in the first rectifying column 313 internal reflux to the first reboilers 311, and isolated 2,4-bis-Tert-butyl phenol steam can be condensed to 2,4-DTBP receiving tank 34 by the first condenser 33 and recycle,Circulating and evaporating 2h obtains antioxidant 168 granulating raw materials of molten state, is transported to middle guarantor the in sprinkling pelleting systemTemperature tank 41, in order to granulation, tests antioxidant 168 granulations of this molten state by the method in HG/T3712-2010Raw material: the light transmittance under 425nm is 99%, the transmitance under 500nm is 99.3%; Main content is 99.3%;2,4-DTBP content is 0.15%; Heating loss is 0.10%.
Antioxidant 168 granulating raw materials of molten state good above-mentioned purification are delivered in granulating working procedure with circulating pump, and this is madeGrain operation is used the sprinkling pelleting system shown in Fig. 4, heat insulation tank 41, thermal insulation pump in the middle of described sprinkling pelleting system comprises42, sprinkling pelleting tower 43, air-introduced machine 47, Blowing stopper 44, cyclone separator 45, sack cleaner 46 and heat exchanger,Heat exchanger comprises 48 and 5 DEG C of water-to-water heat exchangers 49 of Heat Exchanger in Circulating Water System, described sprinkling pelleting tower 43 tower top setting and insulationsThe spray head 431 of the downward spray that pump 42 is connected, the aperture of described spray head is 0.5mm, these spray head 431 peripheriesChuck is set, and described sprinkling pelleting tower 43 arranges respectively air inlet 432 and air outlet 433 near bottom and top; InstituteState air outlet 433 by pipeline successively with described cyclone separator 45, described sack cleaner 46, described air-introduced machine47 and described Heat Exchanger in Circulating Water System 48 and described 5 DEG C of water-to-water heat exchangers 49 be connected; The gas of described 5 DEG C of water-to-water heat exchangers goes outMouth is connected with described air inlet 432 by air inlet pipeline; Described intake air line is provided with wind-warm syndrome survey meter 492 and automaticMend the nitrogen inlet 491 of nitrogen device; Described sprinkling pelleting tower 43 is provided with tower near bottom and presses survey meter 435 and tower to press tuneJoint valve 434; Described Blowing stopper 44 is arranged at sprinkling pelleting tower 43 bottoms;
Described granulating working procedure comprises the steps:
Heat insulation tank 41 in the middle of gained molten state antioxidant 168 granulating raw materials are injected, and by this molten state antioxidantThe temperature of 168 granulating raw materials is controlled at 200～205 DEG C; Air in nitrogen replacement sprinkling pelleting system, makes sprinkling pelletingSystem is nitrogen atmosphere; In described chuck, pass into spray head described in heat-conducting oil heating, control the melting spraying out subsequentlyThe temperature of state antioxidant 168 granulating raw materials is 210～220 DEG C, starts described air-introduced machine 47 and extracts described sprinkling pelletingNitrogen in tower, making the wind speed in described sprinkling pelleting tower is 0.2m/s, and control enters in described sprinkling pelleting towerThe temperature of nitrogen is 10 DEG C; And start thermal insulation pump 42, controlling its operating pressure is 0.35MPa, by middle heat insulation tankMolten state antioxidant 168 granulating raw materials in 41 are squeezed in the spray head 431 of tower top, molten state antioxidant 168Granulating raw material sprays out fine drop downwards by spray head 431, thread shape liquid in the time declining be subject to air-introduced machine 47Deliver to the stream of nitrogen gas contact of the rising in granulation tower, be stripped from into fine drop, fall in process and be cooled to by nitrogenThe antioxidant 168 that the present embodiment pearl shape is granular, falls within granulation tower bottom, then starts Blowing stopper 44, by pearl at the bottom of towerThe granular antioxidant 168 of shape is discharged, and in granulation process, nitrogen is through air outlet 433, cyclone separator 45, pocket typeAfter deduster 46, air-introduced machine 47, Heat Exchanger in Circulating Water System 48 and described 5 DEG C of water-to-water heat exchanger 49 dedustings are cooling through air intakeMouth 432 enters in granulation tower and recycles. Press HG/T3712-2010 and detect, the present embodiment bead shaped particle shape anti-The index of oxidant 168 is as shown in table 2.
Embodiment 2
In 3000L confined reaction, add 2,4-DTBP, the phosphorus trichloride of 253Kg, the 280L of 1108KgToluene solvant and the triethylamine of 4.5Kg after, at 55 DEG C of insulation reaction 1.7h, in 2 hours, be warming up to 125 DEG C,Then at 120～130 DEG C of insulation reaction 3h, steam except reaction dissolvent toluene, stop stirring, then in reactor, add againEnter 1.4m3Toluene, starts and stirs, and reactant is dissolved completely, then obtains through circulating filtration for the first time at 60～85 DEG CTo the pending mother liquor of 2000L, add the potassium hydroxide aqueous solution of 400Kg5%, at 60 DEG C, stir 15 minutes, quietOnly buck was separated in 15 minutes, then added the n-butylamine of 15Kg, at 60 DEG C, stir temperature 15 minutesRise to 70 DEG C, treat that pH is 8～9, the dehydration that heats up, carries out circulating filtration for the second time and must contain when still Wen Wendu reaches 125 DEG CThe mother liquor of antioxidant 168 principal components, presses the method in HG/T3712-2010 by this mother liquor evaporate to dryness to constant weight samplingRecord: 2,4-DTBP content is 3.5%.
By the above-mentioned mother liquid obtained desolvation operation of carrying out, this desolvation operation is used identical with embodiment 1 secondPiece-rate system. In desolvation step, by the second reboiler 211 and the second falling film evaporator 212 conduction oil preheatingTo 230 DEG C, adopt dnockout pump by mother liquid obtained with 2.0m3The speed of/h is steamed by the second falling film evaporator 212Send out, the liquid phase of antioxidant 168 principal components of isolating solvent gas phase and comprising 2,4-DTBP, works as separationAntioxidant 168 crude products of the molten state that contains a small amount of solvent going out reach certain liquid level in the second reboiler 212Time, stop material loading, open the second circulating pump 22, circulating and evaporating approximately 1.5 hours, then starts the second vavuum pump 26,The vacuum that makes the second piece-rate system is-0.02～-0.04MPa, further deviates from after solvent to obtain the antioxidant of molten state168 crude products, antioxidant 168 crude products of this molten state, record by the method in HG/T3712-2010: main containingAmount is 96.3%; 2,4-DTBP content is 3.5%.
Above-mentioned gained molten state antioxidant 168 crude products are sent into refining step, and this refining step uses and embodiment 1The first identical piece-rate system. In refining step step, described the first reboiler 311 and described the first falling liquid film are steamedThe temperature of hair device 312 is increased to 220 DEG C, vacuumizes with vavuum pump, in the time that pressure is less than 3mmHg, through embodiment 1Identical step cycle evaporation 2h, deviates from 2,4-DTBP, obtains molten state antioxidant 168 granulating raw materials,Record by the method in HG/T3712-2010: main content is 99.3%; 2,4-DTBP content is 0.13%;Heating loss 0.15%.
Molten state antioxidant 168 granulating raw materials good above-mentioned purification are delivered in granulating working procedure to this granulation with circulating pumpOperation is used the sprinkling pelleting system identical with embodiment 1, in granulating working procedure step, by anti-oxidant gained molten stateHeat insulation tank 41 in the middle of agent 168 granulating raw materials inject, and by these molten state antioxidant 168 granulating raw material temperature controlsAt 200～205 DEG C, the air in nitrogen replacement sprinkling pelleting system, making sprinkling pelleting system is nitrogen atmosphere; InstituteState and in chuck, pass into spray head described in heat-conducting oil heating, control molten state antioxidant 168 granulations that spray out subsequently formerThe temperature of material is 210～220 DEG C, starts described air-introduced machine 47 and extracts the nitrogen in described sprinkling pelleting tower, makes described sprayThe wind speed drenching in granulation tower is 0.3m/s, and to control the temperature that enters the nitrogen in described sprinkling pelleting tower be 12 DEG C, andStart thermal insulation pump 42, controlling its operating pressure is 0.4MPa, makes this enforcement subsequently by the identical step of embodiment 1The antioxidant 168 of example bead shaped particle shape, detects by HG/T3712-2010, the resisting of the present embodiment bead shaped particle shapeThe index of oxidant 168 is as shown in table 2.
Embodiment 3
In 3000L confined reaction, add the 2,4-DTBP of 1111Kg, the phosphorus trichloride, 267 of 249KgAfter the toluene solvant of L and the pyridine of 5Kg, at 50 DEG C of insulation reaction 3h, in 2 hours, be warming up to 120 DEG C, soAfter at 120～130 DEG C of insulation reaction 3.5h, steam except reaction dissolvent toluene, stop stirring, then in reactor, add againEnter 1.4m3Toluene, starts and stirs, and makes reactants dissolved, then obtains through circulating filtration for the first time at 60～85 DEG CThe pending mother liquor of 2000L, adds the sodium hydrate aqueous solution of 450Kg5%, stirs 20 minutes at 60 DEG C, staticBuck was separated in 30 minutes, then added the triethanolamine of 16Kg, at 75 DEG C, stir temperature 20 minutesRise to 75 DEG C, treat that pH is 8～9, the dehydration that heats up, carries out circulating filtration for the second time and must contain when still Wen Wendu reaches 125 DEG CThe mother liquor of antioxidant 168 principal components, presses the method in HG/T3712-2010 by this mother liquor evaporate to dryness to constant weight samplingRecord: 2,4-DTBP content is 3.9%.
By the above-mentioned mother liquid obtained desolvation operation of carrying out, this desolvation operation is used identical with embodiment 1 secondPiece-rate system. In desolvation step, by the second reboiler 211 and the second falling film evaporator 212 conduction oil preheatingTo 240 DEG C, adopt dnockout pump by mother liquid obtained with 1.5m3The speed of/h is steamed by the second falling film evaporator 212Send out, the liquid phase of antioxidant 168 principal components of isolating solvent gas phase and comprising 2,4-DTBP, works as separationAntioxidant 168 crude products of the molten state that contains a small amount of solvent going out reach certain liquid level in the second reboiler 212Time, stop material loading, open the second circulating pump 22, circulating and evaporating approximately 1.0 hours, then starts the second vavuum pump 26,The vacuum that makes the second piece-rate system is-0.02～-0.04MPa, further deviates from after solvent to obtain the antioxidant of molten state168 crude products, record by the method in HG/T3712-2010: main content is 95.4%; 2,4-DTBP containsAmount is 3.8%.
The antioxidant of above-mentioned gained molten state 168 crude products are sent into refining step, and this refining step uses and embodiment1 the first identical piece-rate system. In refining step step, by described the first reboiler 311 and described the first falling liquid filmThe temperature of evaporimeter 312 is increased to 230 DEG C, vacuumizes with vavuum pump, in the time that pressure is less than 3mmHg, through implementingThe step cycle evaporation 2.5h that example 1 is identical, deviates from 2,4-DTBP, and the antioxidant 168 that obtains molten state is madeGrain raw material, records by the method in HG/T3712-2010: main content is 99.4%; 2,4-DTBP contentBe 0.18%, heating loss is 0.13%.
Molten state antioxidant 168 granulating raw materials good above-mentioned purification are delivered in granulating working procedure to this granulation with circulating pumpOperation is used the sprinkling pelleting system identical with embodiment 1, in granulating working procedure step, by anti-oxidant gained molten stateHeat insulation tank 41 in the middle of agent 168 granulating raw materials inject, and by these molten state antioxidant 168 granulating raw material temperature controlsAt 200～205 DEG C, the air in nitrogen replacement sprinkling pelleting system, making sprinkling pelleting system is nitrogen atmosphere; InstituteState and in chuck, pass into spray head described in heat-conducting oil heating, control molten state antioxidant 168 granulations that spray out subsequently formerThe temperature of material is 210～220 DEG C, starts described air-introduced machine 47 and extracts the nitrogen in described sprinkling pelleting tower, makes described sprayThe wind speed drenching in granulation tower is 0.2m/s, and to control the temperature that enters the nitrogen in described sprinkling pelleting tower be 13 DEG C, andStart thermal insulation pump 42, controlling its operating pressure is 0.35MPa, makes this enforcement subsequently by the identical step of embodiment 1The antioxidant 168 of example bead shaped particle shape, detects by HG/T3712-2010, the resisting of the present embodiment bead shaped particle shapeThe index of oxidant 168 is as shown in table 2.
Embodiment 4
In 3000L confined reaction, add the 2,4-DTBP of 1109Kg, the phosphorus trichloride, 275 of 251KgAfter the toluene solvant of L and the pyridine of 4.5Kg, at 50 DEG C of insulation reaction 1.5h, in 2 hours, be warming up to 128 DEG C,Then at 120～130 DEG C of insulation reaction 2.5h, steam except reaction dissolvent toluene, stop stirring, then in reactor againAdd 1.4m3Toluene, starts and stirs, and makes reactants dissolved, then obtains through circulating filtration for the first time at 60～85 DEG CThe pending mother liquor of 2000L, adds the potassium hydroxide aqueous solution of 400Kg5%, stirs 15 minutes at 60 DEG C, staticBuck was separated in 15 minutes, then added the n-butylamine of 15Kg, at 60 DEG C, stir temperature liter 15 minutesTo 70 DEG C, treat that pH is 8～9, the dehydration that heats up, when still Wen Wendu reach 123 DEG C carry out for the second time circulating filtration must be containing anti-The mother liquor of oxidant 168 principal components, the method that this mother liquor evaporate to dryness to constant weight is pressed in HG/T3712-2010 is surveyed: 2,4-DI-tert-butylphenol compounds content is 2.85%.
By the above-mentioned mother liquid obtained desolvation operation of carrying out, this desolvation operation is used identical with embodiment 1 secondPiece-rate system. In desolvation step, by the second reboiler 211 and the second falling film evaporator 212 conduction oil preheatingTo 240 DEG C, adopt dnockout pump by mother liquid obtained with 1.5m3The speed of/h is steamed by the second falling film evaporator 212Send out, the liquid phase of antioxidant 168 principal components of isolating solvent gas phase and comprising 2,4-DTBP, works as separationAntioxidant 168 crude products of the molten state that contains a small amount of solvent going out reach certain liquid level in the second reboiler 212Time, stop material loading, open the second circulating pump 22, circulating and evaporating approximately 1.0 hours, then starts the second vavuum pump 26,The vacuum that makes the second piece-rate system is-0.02～-0.04MPa, further deviates from anti-oxidant 168 crude products of molten stateSolvent after antioxidant 168 crude products of molten state, record by the method in HG/T3712-2010: main contentBe 95.4%; 2,4-DTBP content is 2.84%.
The antioxidant of above-mentioned gained molten state 168 crude products are sent into refining step, and this refining step uses and embodiment1 the first identical piece-rate system. In refining step step, by described the first reboiler 311 and described the first falling liquid filmThe temperature of evaporimeter 312 is increased to 220 DEG C, vacuumizes with vavuum pump, in the time that pressure is less than 3mmHg, through implementingThe step cycle evaporation 2.0h that example 1 is identical, deviates from 2,4-DTBP, and the antioxidant 168 that obtains molten state is madeGrain raw material, records by the method in HG/T3712-2010: main content is 99.0%; 2,4-DTBP contentBe 0.17%, heating loss is 0.14%.
Molten state antioxidant 168 granulating raw materials good above-mentioned purification are delivered in granulating working procedure to this granulation with circulating pumpOperation is used the sprinkling pelleting system identical with embodiment 1, in granulating working procedure step, by anti-oxidant gained molten stateHeat insulation tank 41 in the middle of agent 168 granulating raw materials inject, and by these molten state antioxidant 168 granulating raw material temperature controlsAt 200～205 DEG C, the air in nitrogen replacement sprinkling pelleting system, making sprinkling pelleting system is nitrogen atmosphere; InstituteState and in chuck, pass into spray head described in heat-conducting oil heating, control molten state antioxidant 168 granulations that spray out subsequently formerThe temperature of material is 210～220 DEG C, starts described air-introduced machine 47 and extracts the nitrogen in described sprinkling pelleting tower, makes described sprayThe wind speed drenching in granulation tower is 0.4m/s, and to control the temperature that enters the nitrogen in described sprinkling pelleting tower be 15 DEG C, andStart thermal insulation pump 42, controlling its operating pressure is 0.35MPa, makes this enforcement subsequently by the identical step of embodiment 1The antioxidant 168 of example bead shaped particle shape, detects by HG/T3712-2010, the resisting of the present embodiment bead shaped particle shapeThe index of oxidant 168 is as shown in table 2.
Embodiment 5
In 3000L confined reaction, add 2,4-DTBP, the phosphorus trichloride of 250Kg, the 265L of 1120KgToluene solvant and the triethylamine of 5Kg after, at 50 DEG C of insulation reaction 1.5h, in 2 hours, be warming up to 120 DEG C, soAfter at 120～130 DEG C of insulation reaction 2.5h, steam except reaction dissolvent toluene, stop stirring, then in reactor, add againEnter 1.4m3Toluene, start stir, antioxidant 168 is dissolved completely, then 60～85 DEG C through for the first time circulateFiltration obtains the pending mother liquor of 2000L, adds the potassium hydroxide aqueous solution of 500Kg5%, stirs 20 points at 75 DEG CClock, separates buck in static 30 minutes, then adds the triethylamine of 12Kg, at 70 DEG C, stir 20 minutes,Temperature rises to 75 DEG C, treats that pH is 8～9, and the dehydration that heats up, carries out circulating filtration for the second time when still Wen Wendu reaches 125 DEG CMust, containing the mother liquor of antioxidant 168 principal components, this mother liquor evaporate to dryness to constant weight sampling be pressed in HG/T3712-2010Method records: 2,4-DTBP content is 3.6%.
By the above-mentioned mother liquid obtained desolvation operation of carrying out, this desolvation operation is used identical with embodiment 1 secondPiece-rate system. In desolvation step, by the second reboiler 211 and the second falling film evaporator 212 conduction oil preheatingTo 230 DEG C, adopt dnockout pump by mother liquid obtained with 1.5m3The speed of/h is steamed by the second falling film evaporator 212Send out, the liquid phase of antioxidant 168 principal components of isolating solvent gas phase and comprising 2,4-DTBP, works as separationAntioxidant 168 crude products of the molten state that contains a small amount of solvent going out reach certain liquid level in the second reboiler 212Time, stop material loading, open the second circulating pump 22, circulating and evaporating approximately 1.5 hours, then starts the second vavuum pump 26,The vacuum that makes the second piece-rate system is-0.02～-0.03MPa, further deviates from antioxidant 168 crude products of molten stateIn solvent after antioxidant 168 crude products of molten state, record by the method in HG/T3712-2010: lead and containAmount is 95.4%; 2,4-DTBP content is 3.6%.
The antioxidant of above-mentioned gained molten state 168 crude products are sent into refining step, and this refining step uses and embodiment1 the first identical piece-rate system. In refining step step, by described the first reboiler 311 and described the first falling liquid filmThe temperature of evaporimeter 312 is increased to 220 DEG C, vacuumizes with vavuum pump, in the time that pressure is less than 3mmHg, through implementingThe step cycle evaporation 2.0h that example 1 is identical, deviates from 2,4-DTBP, and the antioxidant 168 that obtains molten state is madeGrain raw material, records by the method in HG/T3712-2010: main content is 99.1%; 2,4-DTBP contentBe 0.2%, heating loss is 0.15%.
Molten state antioxidant 168 granulating raw materials good above-mentioned purification are delivered in granulating working procedure to this granulation with circulating pumpOperation is used the sprinkling pelleting system identical with embodiment 1, in granulating working procedure step, by anti-oxidant gained molten stateHeat insulation tank 41 in the middle of agent 168 granulating raw materials inject, and by these molten state antioxidant 168 granulating raw material temperature controlsAt 200～205 DEG C, the air in nitrogen replacement sprinkling pelleting system, making sprinkling pelleting system is nitrogen atmosphere; InstituteState and in chuck, pass into spray head described in heat-conducting oil heating, control molten state antioxidant 168 granulations that spray out subsequently formerThe temperature of material is 210～220 DEG C, starts described air-introduced machine 47 and extracts the nitrogen in described sprinkling pelleting tower, makes described sprayThe wind speed drenching in granulation tower is 0.5m/s, and to control the temperature that enters the nitrogen in described sprinkling pelleting tower be 18 DEG C, andStart thermal insulation pump 42, controlling its operating pressure is 0.45MPa, makes this enforcement subsequently by the identical step of embodiment 1The antioxidant 168 of example bead shaped particle shape, detects by HG/T3712-2010, the resisting of the present embodiment bead shaped particle shapeThe index of oxidant 168 is as shown in table 2.
The performance indications of the antioxidant 168 of embodiment 1～5 gained bead shaped particle shape are as shown in table 2:
Table 2
In table 2, granularity order number and bulk density record according to screening method and graduated cylinder method respectively, and described angle of repose adopts to be injectedMethod records.
As can be seen from Table 2, the antioxidant 168 of prepared according to the methods of the invention bead shaped particle shape, its propertyEnergy index reaches the index of 168 industries, and its granularity order number is between 18～80 orders, and its granularity is far longer than prior artThe antioxidant 168 providing, this has not only been avoided dust pollution or blast, and has overcome pulverous anti-oxidantAgent 168, because of the technical problem such as obstruction, wall built-up reinforced and that metering difficulty causes, has improved the production efficiency of Plastic Rubber ProductsAnd quality, in addition, its bulk density is large, and volatility step-down is convenient to packaging, is transported and deposit, and makes to store cost greatlyReduce, make plastic product in forming process, be unlikely to form " flake " and bubble, greatly improved plastic productsQuality.
From embodiment 1～5, can find out, preparation method of the present invention does not have crystallization in traditional handicraft or recrystallizationMethod of purification, has simplified process route, saves great deal of investment, and whole technical process completes under sealing condition,Greatly reduce energy consumption and consumption of raw materials, effectively reduce environmental pollution and raw material can fully be reclaimed, recycle,Production cost significantly reduces.
Finally explanation: above embodiment is only for implementation process of the present invention and feature are described, and unrestricted sent outBright technical scheme, although the present invention is had been described in detail with reference to above-described embodiment, the ordinary skill people of this areaMember is to be understood that: still can modify or be equal to replacement the present invention, and not depart from spirit of the present invention and modelAny modification or partial replacement of enclosing, all should be encompassed in the middle of protection scope of the present invention.

Claims (10)

1. the antioxidant 168 of a bead shaped particle shape, the granularity of the antioxidant 168 of this bead shaped particle shape is10～160 orders; Preferably, the granularity of the antioxidant 168 of described bead shaped particle shape is 18～100 orders, and bulk density is0.4～0.7g/cm3; More preferably, heating loss≤0.2% of described antioxidant 168, and/or angle of repose≤25 °.
2. the preparation method of the antioxidant 168 of bead shaped particle shape claimed in claim 1, the method comprises: adoptBy granulating working procedure, molten state antioxidant 168 granulating raw materials are made to described bead shaped particle shape by sprinkling pelleting systemAntioxidant 168;
Described sprinkling pelleting system comprises thermal insulation pump, sprinkling pelleting tower, air-introduced machine and Blowing stopper, described sprinkling pelleting towerThe tower top setting spray head spraying downwards that is connected with thermal insulation pump, this spray head periphery arranges chuck; Described sprinkling pelleting towerNear bottom and top, air inlet and air outlet are set respectively; Described air-introduced machine is connected with described air outlet by pipeline;Described Blowing stopper is arranged at sprinkling pelleting tower bottom;
Preferably, described sprinkling pelleting system also comprises cyclone separator, sack cleaner and heat exchanger, described air-outMouth is connected with described cyclone separator, described sack cleaner, described air-introduced machine and described heat exchanger successively by pipeline;The gas vent of described heat exchanger is connected with described air inlet by air inlet pipeline;
Described granulating working procedure comprises:
Start described air-introduced machine, from described air inlet by sprinkling pelleting tower described in inert gas suction, in described chuckPass into heat transfer medium and heat described spray head, by described thermal insulation pump by described molten state antioxidant 168 granulating raw materialsSqueeze into described sprinkling pelleting tower and carry out sprinkling pelleting, make the antioxidant 168 of described bead shaped particle shape;
Preferably, the inert gas of extracting out from air outlet successively through described cyclone separator, sack cleaner, air-introduced machine,Heat exchanger enters sprinkling pelleting tower by described air inlet circulation.
3. method according to claim 2, wherein, the aperture of described spray head is 0.1～1mm; Described sprayThe height that drenches granulation tower is 10～30m;
Start described air-introduced machine, the wind speed of controlling in described sprinkling pelleting tower is 0.1～1m/s; And control enter described inThe temperature of the inert gas in sprinkling pelleting tower is 10～20 DEG C;
In described chuck, pass into heat transfer medium and heat described spray head, control the molten state antioxidant 168 spraying outThe temperature of granulating raw material is 210～250 DEG C;
The operating pressure of controlling described thermal insulation pump is 0.2～0.8MPa.
4. method according to claim 2, wherein, the heating loss of described antioxidant 168 granulating raw materials≤0.2％；
Preferably, these antioxidant 168 granulating raw materials are to be steamed except the tertiary fourth of 2,4-bis-by molten state antioxidant 168 crude productsBase phenol obtains; More preferably, main content >=90% of these antioxidant 168 crude products, 2,4-DTBPContent≤10%.
5. method according to claim 4, wherein, adopts the first piece-rate system to steam except 2,4-DTBP;Described the first piece-rate system comprises the first reboiler, the first falling film evaporator, the first rectifying column, the first circulating pump andOne vavuum pump; The bottom of the bottom of described the first falling film evaporator and the first rectifying column is separately positioned on described first and boilsDevice top is also attached thereto respectively logical; The outlet at bottom of the import of described the first circulating pump and described the first reboiler passes throughPipeline is connected, and described the first circulation delivery side of pump is connected by pipeline with the top entrance of described the first falling film evaporatorConnect; Described the first vavuum pump is connected with described the first rectifying column tower top;
Preferably, adopt described the first piece-rate system to steam except 2,4-DTBP by refining step, described refiningOperation comprises the steps:
(1) open described vavuum pump, reduce the pressure of described the first piece-rate system, and described the first reboiler that raisesTemperature with described the first falling film evaporator;
(2) by product pump, described molten state antioxidant 168 crude products being delivered to described the first falling film evaporator entersRow evaporation, utilizes described the first circulating pump and described the first falling film evaporator to carry out circulating and evaporating, and utilizes described firstRectifying column separates and obtains described antioxidant 168 granulating raw materials and 2,4-DTBP;
More preferably, in step (1), open described the first vavuum pump, by described the first piece-rate system Pressure DropBe low to moderate and be less than or equal to 5mmHg, and the temperature of described the first reboiler and described the first falling film evaporator is raise respectivelyTo 200～250 DEG C.
6. method according to claim 4, wherein, described antioxidant 168 crude products are by 2,4-di-t-butylThe reactant containing antioxidant 168 principal components that phenol and phosphorus trichloride synthetic method make obtains through post processing, described inPost processing comprise first stage and second stage:
The described first stage is included in and in described reactant, adds cosolvent solubilizing reaction thing, and filter, wash,Add organic base and dehydration to obtain the process containing the mother liquor of antioxidant 168 principal components;
Described cosolvent be can make described reactants dissolved and can with the solvent of water azeotropic, preferably toluene and/or dimethylbenzene;
Described second stage is the solvent steaming except in described mother liquor.
7. method according to claim 6, wherein, the described first stage is included in described reactant and addsAfter entering cosolvent solubilizing reaction thing, filter for the first time successively, inorganic base washing, add organic base, dehydration andFilter for the second time, obtain described mother liquor;
Preferably, adding organic base to make system pH is 7.5～11; More preferably, described organic base comprise n-butylamine,One or more in triethanolamine and triethylamine.
8. method according to claim 7, wherein, second stage adopts the second piece-rate system to steam except described motherSolvent in liquid;
Wherein, described the second piece-rate system comprises the second reboiler, the second falling film evaporator, Second distillation column, secondCirculating pump; The bottom of described the second falling film evaporator and the bottom of Second distillation column are separately positioned on described the second reboilerTop is also attached thereto respectively logical; The outlet at bottom of the import of described the second circulating pump and described the second reboiler is by pipeRoad is connected, and described the second circulation delivery side of pump is connected by pipeline with the top entrance of described the second falling film evaporatorConnect;
Optionally, described the second piece-rate system also comprises the second vavuum pump, described the second vavuum pump and described the second rectifyingThe tower top of tower is connected;
Preferably, adopt the second piece-rate system to steam except the solvent in described mother liquor by desolvation operation, described in removeSolvent operation comprises the steps:
(A) the raise temperature of described the second reboiler and described the second falling film evaporator;
(B) described mother liquor is evaporated by described the second falling film evaporator, utilize described the second circulating pump and instituteState the second falling film evaporator described mother liquor is carried out to circulating and evaporating, and it is described anti-to utilize described Second distillation column separation to obtainSolvent in oxidant 168 crude products and mother liquor;
Optionally, in the time that described the second piece-rate system comprises described the second vavuum pump, described desolvation operation also comprisesStep (C);
(C) open described the second vavuum pump, reduce the pressure of described the second piece-rate system, identical by step (B)The further desolvation of mode.
9. method according to claim 8, wherein, in step (A), by described the second reboiler and instituteThe temperature of stating the second falling film evaporator rises to respectively 200～250 DEG C;
In step (B), described mother liquor is evaporated continuously to charging rate by described the second falling film evaporatorBe 1～3m3/h；
Optionally, in the time that described desolvation operation comprises step (C), open described the second vavuum pump, described in inciting somebody to actionThe pressure decreased of the second piece-rate system to vacuum is 0～-0.08MPa.
10. bead shaped particle antioxidant 168 claimed in claim 1 is adding plastics to as auxiliary antioxidantIn application.
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