CN106883876A - A kind of sweating and the method that PUR wax is produced with F-T synthetic products - Google Patents
A kind of sweating and the method that PUR wax is produced with F-T synthetic products Download PDFInfo
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- CN106883876A CN106883876A CN201510928614.0A CN201510928614A CN106883876A CN 106883876 A CN106883876 A CN 106883876A CN 201510928614 A CN201510928614 A CN 201510928614A CN 106883876 A CN106883876 A CN 106883876A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/36—Recovery of petroleum waxes from other compositions containing oil in minor proportions, from concentrates or from residues; De-oiling, sweating
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/42—Refining of petroleum waxes
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Abstract
A kind of method that PUR wax is produced the invention discloses sweating and with F-T synthetic products.The method carries out hydro-conversion with F-T synthetic products that n-alkane weight content is more than 85% as raw material under catalyst action；Hydrogenation products produce purpose product through sweating again.The inventive method is on the basis of common sweating process, solid mass is placed in wax layer pressure is applied to wax layer in sweating effort, and liquid composition is carried out by wax layer using air-flow, enhance the separating effect of solids fraction and liquid composition and accelerate separating rate.The inventive method has the advantages that investment of production equipment is low, production process is simple and operating cost is low, safety, energy-conservation and solvent-free pollution, and products therefrom can be used as PUR wax.
Description
Technical field
The method that PUR wax is produced the invention belongs to Wax special production technical field, more particularly to a kind of sweating and with F-T synthetic products.
Background technology
PUR is a kind of adhesive of plasticity, and its physical state changes and changes with temperature in certain temperature range, and chemical characteristic is constant, and its is nonpoisonous and tasteless, belongs to environmentally friendly chemicals；Product is solid, is easy to pack, transports, stores, while have simple production process, the advantages of applying glue is convenient, bonding strength is big, speed is fast thus be used widely in many fields.With ethene-vinyl acetate random copolymer（EVA）Based on the EVA hot-melt adhesive of resin be the most important kind of PUR.
EVA hot-melt adhesive is by basic resin, tackifying resin, viscosity modifier and antioxidant etc. into being grouped into.Basic resin is EVA resin, and its ratio, quality determine the key property of PUR（Cementitiousness, melt temperature and adhesion strength such as glue）.Tackifying resin can improve the mobility and the wetability to adherend of colloid, improve adhesive property, reach required adhesion strength.Tackifying resin mainly has rosin, modified rosin, C5 Petropols, C9 Petropols, terpene resin etc..The effect of viscosity modifier is mobility, the regulation setting rate for increasing colloid molten state, to reach the quick purpose being firmly bonded.Viscosity modifier is typically chosen paraffin, microwax, synthetic wax etc..Antioxidant is to prevent the premature aging of EVA hot-melt adhesive, it is ensured that adhesive property does not change under the high temperature conditions.The cold-resistance agent of some suitable frigid zone temperature or the antiheat agent of suitable torrid zone temperature can also be mixed in addition to several raw materials according to the difference of temperature, area more than, some occasions can also add a small amount of filler to increase interstitial and reduces cost.
The viscosity and mobility of PUR are closely related with sizability.Maximum to PUR applying glue viscosity influence is viscosity modifier, i.e. wax.Because wax is the composition of viscosity minimum in PUR, the consumption for increasing wax can significantly reduce the viscosity of PUR, increase its mobility.Mainly consider its fusing point, crystallinity, oil content, viscosity, molecular vibrational temperature and molecular structure during selection wax.The fusing point of synthetic wax is high, is widely used in requiring resistant to elevated temperatures PUR product.
Fischer-Tropsch（F-T）Synthetic technology is nineteen twenty-three invention, mainly includes high temperature synthesis techniques and low temperature synthesis technique, and F-T synthesis techniques and catalyst all achieve breakthrough progress since nineteen nineties, and F-T sinteticses become increasingly abundant.In F-T synthetic product chemical compositions based on n-alkane, there is a small amount of isoparaffin, its melt viscosity is low, crystallinity is high under solid-state, the wax product of high-melting-point, high rigidity can be prepared, but contain more alkene and oxygenatedchemicals in F-T synthetic products, and carbon number distribution is very wide, in being not suitable for being directly used in and requiring resistant to elevated temperatures PUR product.
The general name of the pertroleum wax obtained all kinds of wax products that are crude oil after refining processing from wax-containing distillate, including atoleine, soap manufacturing paraffin, paraffin and microwax.Pertroleum wax is the mixture of the components such as various n-alkanes, isoparaffin and cycloalkane.
In terms of pertroleum wax production technology, conventional pertroleum wax separates manufacturing process mainly distillation, solvent are separated, sweating is separated etc..
Distillation is the purpose that separating-purifying is reached using the boiling point difference of different hydrocarbons, and reducing the boiling range of distillation can effectively reduce the width of product carbon distribution, but still-process needs to be heated to raw material more than boiling point, consume substantial amounts of energy.The boiling point of hydro carbons of the fusing point more than 70 DEG C is at 500 DEG C simultaneously（Normal pressure）More than, efficiency is greatly reduced when being separated using distillation.
Solvent fractionation method is the purpose that separating-purifying is reached using n-alkane and isoparaffin different solubility in a solvent, the normal paraffin content in product can be effectively improved, but the width influence on carbon distribution is little, while solvent separating technology investment of production equipment is big；Needed in production process largely using solvent, recycling design needs to consume substantial amounts of energy；Contain benzene homologues in solvent, environment can be impacted；Solvent is inflammable, easily causes production accident.
Sweating separation method is to carry out separating-purifying using the different property of various component fusing points in wax.The molecular weight of various components and structure Bu Tong can all make its fusing point different in pertroleum wax.When being all n-alkane, the fusing point of the larger n-alkane of molecular weight is higher, and the fusing point of the less n-alkane of molecular weight is relatively low；When molecular weight is identical, the fusing point of isoparaffin and cycloalkane will be less than n-alkane, and isomery degree more high-melting-point is lower.
Compared with distillating method, because the melting temperature of various hydro carbons is far below boiling temperature, so the energy consumption of sweating separation process is far below separated；Compared with solvent fractionation method, sweating separation process does not use solvent, thus sweating separation process safety, energy-conservation and on environment without influence.
Common sweating process is mainly included the following steps that：（1）Preparation：Pad water, sweatbox ware plate lower space is full of with water；Charging, loads sweatbox when raw material is heated to more than fusing point being in a liquid state；（2）Crystallization：Raw material is progressively cooled to 10~20 DEG C below its fusing point with being not more than the rate of temperature fall of 4 DEG C/h.In cooling procedure, order of the various components by fusing point from high to low crystallizes to form solid successively；（3）Sweating：After wax layer temperature reaches default cooling final temperature, pad water is bled off；Raw material is lentamente heated to default sweating final temperature again.In sweating effort, order of the various components by fusing point from low to high is successively fused into liquid and flows out（Under wax）, the wax layer residue for finally obtaining（On wax）It is exactly high-melting-point, the wax of low oil-containing；Sweating effort terminates follow-up high-temperature of continuing rising, is taken out on wax with melting, as crude product；（4）It is refined：Predetermined temperature is warming up to after crude product fusing, carclazyte is added and constant temperature is stirred to the scheduled time filtering, then be purpose product through shaping, packaging.
To common sweating separation method, the solids fraction in intensification sweating effort（The wax of higher melt）And liquid composition（Oil and compared with the wax of low melting point）Although being respectively at two kinds of phases of solid and liquid, it also is difficult to be kept completely separate.It is usual to use extension sweating sessions and improve the method for sweating final temperature for the oil content for making final products meets the requirements, but can so cause the production cycle long and product yield decline.
Common sweating separating technology can produce fusing point soap manufacturing paraffin and low melt point paraffin with thick flaky crystal structure under 40 DEG C~60 DEG C of solid-state, be not suitable for producing wax product of the fusing point more than 70 DEG C.Experiment shows, common sweating process produces fusing point in 70 DEG C or so of wax product, the carbon dispersion of distribution and oil content on sweating later stage wax is unrelated with yield, the carbon dispersion of distribution and oil content i.e. on wax do not decline with the decline of yield, so so far there are no producing report of the fusing point in 70 DEG C or so of wax product with sweating separating technology.
Compared with solvent is separated, sweating separating technology is intermittently operated, and product yield is relatively low, the production cycle is more long, but sweating separating technology has the advantages that small investment, production process are simple, operating cost is low, production process safety, energy-conservation and environmentally safe, still has part producer producing soap manufacturing paraffin product using the method at present.
For many years, sweating method has obtained some development, such as CN89214332 in production equipment and process aspect（Vertical square multipul sections spacer diaphoresis tank）、CN94223980.6（Ware type sudorific device）、CN98233254.8（Paraffin sweating pot）、CN200920033500.X（Novel paraffin sweating tank）、CN201210508905.0（A kind of Efficient paraffin sweatbox）、CN201320127680.4（Tubular type paraffin deoiler）Etc. patent, improved in sweating production equipment；CN91206202（A kind of high-efficient sweat pot for paraffin wax）Improved on sweating separating technology, but these improvement can not still produce wax product of the fusing point more than 70 DEG C.
Sweating separating technology is to be currently known the unique solvent-free separation method for commercial scale petroleum paraffin product, is advocating today of green low-carbon, environmental protection and energy saving, and the demand using sweating separating technology production PUR wax is more urgent.
The content of the invention
In view of the shortcomings of the prior art, a kind of method that the present invention is provided sweating and PUR wax is produced with F-T synthetic products, including hydro-conversion and sweating two parts.Specifically with suitable F-T synthetic products as raw material, hydro-conversion is carried out under catalyst action, alkene therein and oxygenatedchemicals are converted into n-alkane；Sweatbox is used again, on the basis of common sweating process, increases the constant temperature stage of sweating effort；Liquid composition is carried out to force to separate solids fraction and liquid composition by wax layer using air-flow in sweating effort, separating effect is enhanced and is accelerated separating rate.Pressure is applied to accelerate the separating rate of solids fraction and liquid composition and ensure airflow through wax layer to wax layer preferably by way of placing solid mass in wax layer in sweating effort, this solvent-free separation method of sweating is produced product of the melt drop temperature more than 70 DEG C.The inventive method has the advantages that investment of production equipment is low, production process is simple and operating cost is low, safety, energy-conservation and solvent-free pollution.
A kind of sweating of the invention and the method that PUR wax is produced with F-T synthetic products, including herein below：
（One）Hydro-conversion：F-T synthetic products carry out hydro-conversion under catalyst action, and alkene therein and oxygenatedchemicals are converted into n-alkane；
（Two）Sweating：Including procedure below：
（1）Charging：With process（One）Hydroconverted products be raw material, heating fusing after load sweatbox；
（2）Crystallization：Wax layer is cooled to 5 DEG C~30 DEG C below raw material melt drop temperature of cooling final temperature with the speed of 2.0 DEG C/h~4.0 DEG C/h；
（3）The sweating of intensification-constant temperature：Heated up with the speed of 1.5 DEG C/h~3.5 DEG C/h, wax layer reaches predetermined temperature and constant temperature stops sweating afterwards for a period of time, and wax layer is forced air flow through in sweating effort；
（4）It is refined：On wax PUR wax product is after refined, shaping, packaging.
In the method for the present invention, described F-T synthetic products, more than 80%, preferably F-T synthetic product of the normal paraffin content more than 90% is used as raw material for the requirement of its n-alkane weight content.
In the method for the present invention, process（One）Described hydroconversion process uses the ordinary skill in the art, and its operating condition is：The h of volume space velocity 0.2~2.0 when 3~10MPa of reaction pressure, 150~300 DEG C of reaction temperature, liquid-1With hydrogen liquid volume ratio 100~1000：1, hydrogen liquid volume ratio is preferably 300~800：1.Hydrogenation conversion catalyst can be Ni/Al2O3、W-Ni/Al2O3、Mo-Ni/Al2O3Or W-Mo-Ni/Al2O3Catalyst etc..In catalyst active metal component with the weight content that oxide is counted be 20%~70%.Hydrogenation conversion catalyst can be prepared by this area conventional method.Reactive metal oxides can be reduced or vulcanized by catalyst by this area conventional method as needed when using, to improve catalyst activity.
In the method for the present invention, in step（3）In sweating effort, solid mass preferably is placed to apply the pressure of more than 0.5kPa to wax layer by wax layer surface.Solid mass surfacing, overall dimensions are slightly less than sweatbox inner wall size（Such as, solid mass edge is generally 0.01~50mm, preferably 0.1~20mm with the gap of sweatbox inwall）, inside have the space run through up and down.The density of solid mass typically requires to be more than 4g/cm3, can be the materials such as nonmetallic, metal and alloy, preferred density is 6~12g/cm3Metal and alloy, such as zinc, iron, copper, lead and its more stable low price metal material of alloy chemical property.Solid mass can apply the pressure of more than 0.5kPa, preferably 1.4~20.0kPa to wax layer.
In the present invention, solid mass can be placed on wax layer surface one of in the following ways and apply pressure with to wax layer（Pressure）：（1）It is disposable in sweating effort to add the solid mass that produce more than 0.5kPa pressure, it is disposable preferably when sweating starts to add the solid mass that produce 1.4~20.0kPa pressure；（2）In sweating effort several times（It is preferred that 2~3 times）Add, i.e., being added in every 0.1~20.0 h can produce more than 0.5kPa pressure（Pressure）Solid mass, being added preferably in every 0.1~10.0 h can produce the solid mass of 1.4~10.0kPa pressure.
In the method for the present invention, described sweatbox is sweating ware, and increases vacuum plant in wax layer pressue device added above and/or below wax layer.In step（3）In sweating effort, it is described force air flow through wax layer and use increase above wax layer air pressure and/or air pressure is reduced below wax layer, wax layer upper and lower is formed pressure difference and realize.Described pressure（Pressure）Difference is generally 10~500 kPa, preferably 20~200kPa, to force air flow through wax layer.
In the method for the present invention, the step（2）The rate of temperature fall of crystallization preferably 2.5 DEG C/h~3.5 DEG C/h.Described cooling final temperature is preferably 10 DEG C~20 DEG C below raw material melt drop temperature.
In the method for the present invention, the step（3）Sweating effort heating rate preferably 2.0 DEG C/h~3.0 DEG C/h；The predetermined temperature of the intensification is purpose product melt drop temperature -10 DEG C~purpose product melt drop temperature；It is described be warming up to preset temperature after, increase the constant temperature stage so that solids fraction is separated more fully with liquid composition, the time in constant temperature stage is 0~5.0 hour, preferably preferably 0.1~5.0 hour, 1.0~5.0 hours.
In the method for the present invention, the programming rate and cooling rate of said wax layer can be controlled, it is preferred to use oil bath by air bath, oil bath or other feasible modes.When controlling wax layer heating rate and rate of temperature fall using oil bath mode, chuck can be increased outside sweating ware, chuck is connected with removable coil pipe and the circulatory system, the circulatory system has programmed cooling/heating function, the circulatory system adds conduction oil as circulatory mediator；Coil pipe is submerged and is fixed in wax layer after charging, can make wax layer lifting/lowering temperature process faster, wax layer more uniform temperature.
In the method for the present invention, the step（3）Force air flow through wax layer and can implement in sweating effort any stage, preferably implement at the sweating initial stage.
In the method for the present invention, the step（3）Force air flow through wax layer be utilized in wax layer top increase air pressure realize, 20~200 kPa can be such as applied above wax layer（Gauge pressure）Air pressure, and wax layer lower section remain normal pressure.
In the method for the present invention, the step（3）The wax layer that forces air flow through be utilized in wax layer lower section and reduce what air pressure was realized, air pressure that such as can be above wax layer keeps normal pressure, and -20~-80 kPa are maintained below wax layer（Gauge pressure）Air pressure.
Analysis shows, the not impurity such as sulfur-bearing, nitrogen, aromatic hydrocarbons in F-T synthetic products based on n-alkane and is distributed very wide in chemical composition, and contains a small amount of alkene and oxygenatedchemicals.The melt viscosity of this product is low, and this can make high temperatures be deteriorated to being beneficial as PUR wax due to there is olefin component；Oxygenatedchemicals has special smell；Resistance to elevated temperatures drastically declines when a large amount of low-melting components make it be used in PUR product, therefore F-T synthetic products are not suitable for being directly used as the viscosity modifier of PUR product.
Sweating separation method is separated using the different property of various component fusing points.Research for sweating effort shows that liquid composition is gradually discharged along crystalline portion in sweating effort, similar to the situation that liquid flows in capillary.But the high melting-point wax for fusing point at 70 DEG C or so, because raw material chemical composition is complicated, cause the tiny densification of crystals upon crystallization structure, discharge to liquid composition forms huge filter flow resistance power, this results in and only is difficult to be kept completely separate with liquid composition by solids fraction in the common sweating effort of gravity natural separation, therefore common sweating separating technology can not produce wax product of the fusing point more than 70 DEG C.
The present invention is in order to produce PUR wax product, by the further investigation of the composition to F-T synthetic products, contain a certain amount of alkene and oxygenatedchemicals for it, and the non-constant width of carbon number distribution is to cause it to be not suitable for the reason for being directly used as PUR wax, by selecting appropriate catalyst and reaction condition, the components such as alkene and oxygenatedchemicals are converted into n-alkane.By the further investigation to common sweating effort, it is difficult to separate reason for solids fraction and liquid composition, used in sweating effort and force air flow through wax layer, pressure further preferably is being applied to wax layer by way of placing solid mass on wax layer surface in sweating effort simultaneously, and increase the processes such as the constant temperature stage of sweating effort, effectively removal low-melting component, makes the performance of product disclosure satisfy that the requirement of PUR wax.
The reason for separating is difficult to liquid composition for solids fraction in sweating effort, forces liquid composition to be separated with solids fraction by the method that wax layer carries out liquid composition using air-flow by sweating effort, enhanced separating effect and accelerate separating rate；During common sweating process, with the gradually discharge of liquid composition, wax layer can produce the contraction of vertical direction and the contraction of horizontal direction, when pressure difference is formed to force air flow through wax layer up and down in wax layer, it some times happens that air-flow flows through and without the phenomenon of wax layer through gap between wax layer and ware plate.In the inventive method, pressure is applied to wax layer by way of placing solid mass on wax layer surface, the liquid composition coated in extrudable wax crystallization is so as to accelerate the separating rate of solids fraction and liquid composition, prior can be to make wax layer only produce the contraction of vertical direction without the contraction of generation horizontal direction, increase the resistance between wax layer and baffle plate and ware plate；Simultaneously because there is the space run through up and down inside solid mass, it can be ensured that air-flow passes through wax layer to carry out liquid composition.Being aided with the constant temperature stage of sweating effort again makes solids fraction that the method such as more abundant is separated with liquid composition so that sweating separating technology can produce PUR wax product.
This have the advantage that：By selecting appropriate catalyst and reaction condition, the alkene and oxygenatedchemicals in raw material can be converted into n-alkane by hydrogenation process；The separating effect of solids fraction and liquid composition by the method that wax layer carries out liquid composition is enhanced using air-flow and separating rate is accelerated；Solid mass is placed to accelerate the separating rate of solids fraction and liquid composition and ensure airflow through wax layer by wax layer in sweating effort simultaneously, so that sweating separating technology can produce PUR wax product.The method of the present invention has the advantages that plant investment is low, production process is simple and operating cost is low, safety, energy-conservation and solvent-free pollution environment.
Specific embodiment
The present invention is raw material by from suitable F-T synthetic products, and hydro-conversion is carried out under catalyst action；Sweating ware top connects dismountable sealing device and is connected with pressurized buffer tank and compressor, and/or connects pressure-reducing cushioning tank and vavuum pump in sweating ware bottom；Load sweating ware after hydrogenation products heating fusing；Wax layer heating-cooling speed is controlled with oil bath；In sweating effort, start compressor with wax layer malleation formed above, and/or start vavuum pump in wax layer negative pressure formed below, to be used to force air flow through wax layer；Preferably gradually increase solid pressure on wax layer surface in sweating effort；Wax layer temperature reaches preset temperature and constant temperature stops sweating effort afterwards for a period of time；On wax PUR wax product is after refined, shaping, packaging.
The method that 1-2 is illustrated sweating of the invention and PUR wax is produced with F-T synthetic products by the following examples.
Embodiment
1
The present embodiment includes：（One）Hydro-conversion and（Two）Sweating two parts.
（One）Hydro-conversion
With the wax oil product of Sinopec Group's low temperature F-T compound experiment devices（Normal paraffin content is 95.5wt%）It is raw material, in FHJ-2 catalyst（A kind of Ni/Al2O3Commercial catalysts, Fushun Petrochemical Research Institute's development and production count active metal nickel content as 40 wt% with oxide, and catalyst is using preceding carrying out conventional reduction treatment）Under effect, in reaction pressure 5.0MPa, 200 DEG C of reaction temperature, the h of volume space velocity 1.0-1With hydrogen liquid volume ratio 500：It is hydrogenated with conditions of 1, to convert alkene therein and oxygenatedchemicals.
Hydrogenation products property：N-alkane weight content 97.36%；85.0 DEG C of melt drop temperature；Needle penetration（25℃）57（10-1mm）；Chromatogram-mass spectral analysis, does not detect the materials such as alcohol, alkene, acid.
Never the material such as detection alcohol, alkene, acid can be seen that the oxygenatedchemicals in raw material is removed substantially；From needle penetration（25℃）57（10-1mm）It can be seen that containing a large amount of low melting points in hydrogenation products.
（Two）Sweating
This part includes：（1）Preparation,（2）Crystallization,（3）The sweating of intensification-constant temperature,（4）The processes such as product purification.
（1）Preparation
By sweating ware（Inwall is the square of 1m × 1m）Sealing system connected with pressurized buffer tank and compressor；Pressure-reducing cushioning tank is installed in sweating ware bottom and vavuum pump is connected；Sweating ware chuck and removable coil pipe are connected with the circulatory system, with conduction oil as medium；Start the heating function of the circulatory system, conduction oil is warming up to 90 DEG C.
Sweating ware ware plate lower section pad water.With（One）The hydrogenation products for obtaining are raw material, and sweating ware is added after heating fusing.Coil pipe is immersed in raw material wax layer and fixed.
（2）Crystallization
Start the refrigerating function of the circulatory system, wax layer temperature drop to 71.0 DEG C is made with the rate of temperature fall of 3.0 DEG C/h；Close the refrigerating function of the circulatory system.
（3）The sweating of intensification-constant temperature
Discharge sweating ware pad water.Sweating ware outlet connection intermediate storage tank（Ⅰ）To receive under wax；Connection sweating ware sealing device for upper portion of annular；Start compressor and keep pressurized buffer tank internal pressure strong stability in 140~160kPa（Gauge pressure）, sweating ware ware plate lower section keeps normal pressure；Start circulation system function, wax layer temperature is increased to 85.0 DEG C with the heating rate of 2.5 DEG C/h.Stop compressor, remove sealing device.
Open vavuum pump and keep surge tank internal pressure strong stability in -50~-70 kPa（Gauge pressure）, wax layer top air pressure holding normal pressure；Continue to make wax layer temperature be increased to 95.0 DEG C and constant temperature 4.0 hours so that the solids fraction in wax layer is sufficiently separated with liquid composition with the heating rate of 2.5 DEG C/h.Stop vavuum pump, terminate sweating effort.
Sweating ware exports changing-over crude product storage tank（Ⅰ）To receive on wax；Continue the temperature of rising conduction oil to 110 DEG C, taken out on wax with melting, as crude product（Ⅰ）.
（4）Product purification
Crude product（Ⅰ）PUR wax product is after clay-filtered, shaping, packaging（Ⅰ）.
PUR wax product（Ⅰ）Property：95.9 DEG C of melt drop temperature；Needle penetration（25℃）2（10-1mm）；PUR wax product（Ⅰ）Yield is 12.3%（Relative to raw material hydrogenation products）.
From needle penetration（25℃）2（10-1mm）It can be seen that low melting point is removed substantially in hydrogenation products.
Embodiment
2
The present embodiment includes：（One）Hydro-conversion,（Two）Sweating two parts.
（One）Hydro-conversion
With embodiment 1.
（Two）Sweating
This part includes：（1）Preparation,（2）Crystallization,（3）The sweating of intensification-constant temperature,（4）The processes such as product purification.
（1）Preparation
Prepare stainless steel plate some, every piece of stainless steel plate overall dimensions are 0.98 m × 0.98m × 0.02 m, and bore the through hole of the m of equally distributed φ 0.0015 on stainless steel（Drilling, hole center spacing 0.04m are played at edge 0.01m）（The pressure about 1.5kPa that every piece of stainless steel plate is produced）, it is standby.
By sweating ware（With embodiment 1）Sealing system connected with pressurized buffer tank and compressor；Pressure-reducing cushioning tank is installed in sweating ware bottom and vavuum pump is connected；Sweating ware chuck and removable coil pipe are connected with the circulatory system, with conduction oil as medium；Start the heating function of the circulatory system, conduction oil is warming up to 90 DEG C.Sweating ware ware plate lower section pad water.
With（One）Middle hydrogenation products are raw material, and sweating ware is added after heating fusing.Coil pipe is immersed in raw material wax layer and fixed.
（2）Crystallization
Start the refrigerating function of the circulatory system, wax layer temperature drop to 71.0 DEG C is made with the rate of temperature fall of 3.0 DEG C/h.Close the refrigerating function of the circulatory system.
（3）The sweating of intensification-constant temperature
Discharge sweating ware pad water.Sweating ware outlet connection intermediate storage tank（Ⅱ）To receive under wax；First piece of foregoing stainless steel plate of horizontal positioned on wax layer surface；Connection sweating ware sealing device for upper portion of annular；Start compressor and keep pressurized buffer tank internal pressure strong stability in 140~160kPa（Gauge pressure）, sweating ware ware plate lower section keeps normal pressure；Start circulation system function, wax layer temperature is increased to 85.0 DEG C with the heating rate of 2.5 DEG C/h.Stop compressor, remove sealing device.
Second piece of foregoing stainless steel plate is placed on wax layer surface；Start vavuum pump and keep surge tank internal pressure strong stability in -50~-70 kPa（Gauge pressure）, wax layer top air pressure holding normal pressure；Continuation makes wax layer temperature be increased to 95.0 DEG C with the heating rate of 2.5 DEG C/h；The 3rd piece of foregoing stainless steel plate is placed on wax layer surface；And constant temperature 4.0 hours is so that the solids fraction in wax layer is sufficiently separated with liquid composition.Stop vavuum pump, terminate sweating effort.
The outlet of sweating ware is changed to connect crude product storage tank（Ⅱ）To receive on wax.Continue to raise circulating water temperature to 110 DEG C, taken out on wax with melting, as crude product（Ⅱ）.
（4）Product purification
Crude product（Ⅱ）PUR wax product is after clay-filtered, shaping, packaging（Ⅱ）.
PUR wax product（Ⅱ）Property：94.6 DEG C of melt drop temperature；Needle penetration（25℃）1（10-1mm）；PUR wax product（Ⅱ）Yield is 16.5%（Relative to raw material hydrogenation products）.
From needle penetration（25℃）1（10-1mm）It can be seen that low melting point is removed substantially in hydrogenation products.
Comparative example
1
By this area conventional method, the wax oil product for being synthesized with low temperature F-T respectively（The raw material of hydrogenation process in embodiment）, the product of embodiment 1 and the product of embodiment 2 prepare PUR sample as viscosity modifier, test dispensing（Parts by weight）As shown in table 1.
Table 1 tests dispensing.
Oil bath is warming up to 140 DEG C, wax, rosin, terpene resin and antioxidant is added after temperature is constant in reaction bulb, stirring to solid material is completely melt, then the addition EVA that heats up, stir PUR sample is obtained until completely melted.
Above-mentioned properties of sample is determined, as a result as shown in table 2.
The properties of sample of table 2.
Be can be seen that from above-mentioned performance comparison and the PUR sample of the product of example 1 and the preparation of the product of embodiment 2 is applied without obvious smell by the present invention, illustrate that material is smelt in the cause that hydrogenation process is effectively eliminated in the wax oil product of F-T synthesis；During the PUR use in the range of most important 160~180 DEG C the apparent viscosity of three quite, the apparent viscosity at a temperature of other is also basically identical；And on softening point, the PUR sample that PUR sample prepared by the product of example 1 and the product of embodiment 2 is prepared apparently higher than the wax oil product that F-T synthesize is applied by the present invention, illustrate that the product for producing of the invention is suitable for use as PUR wax.
The method that can be seen that sweating of the present invention by embodiment 1-2 and PUR wax is produced with F-T synthetic products, by selecting appropriate catalyst and reaction condition, n-alkane is converted into by the alkene and oxygenatedchemicals in raw material；By increasing the improvement to sweatbox such as pressurization and/or vacuum facility；By placing solid mass in wax layer, and the improvement to sweating process such as wax layer, the constant temperature stage for increasing sweating effort is forced air flow through in sweating effort；Enhance the separating effect of solids fraction and liquid composition and accelerate separating rate, so that sweating separating technology produces PUR wax product of the melt drop temperature more than 70 DEG C.
Claims (21)
1. a kind of sweating and the method that PUR wax is produced with F-T synthetic products, including herein below：
（One）Hydro-conversion：F-T synthetic products carry out hydro-conversion under catalyst action, and alkene therein and oxygenatedchemicals are converted into n-alkane；
（Two）Sweating：Including procedure below：
（1）Charging：With process（One）Hydroconverted products be raw material, heating fusing after load sweatbox；
（2）Crystallization：Wax layer is cooled to 5 DEG C~30 DEG C below raw material melt drop temperature of cooling final temperature with the speed of 2.0 DEG C/h~4.0 DEG C/h；
（3）The sweating of intensification-constant temperature：Heated up with the speed of 1.5 DEG C/h~3.5 DEG C/h, wax layer reaches predetermined temperature and constant temperature stops sweating afterwards for a period of time, and described predetermined temperature is purpose product melt drop temperature -10 DEG C~purpose product melt drop temperature；Wherein, wax layer is forced air flow through in sweating effort；
（4）It is refined：On wax PUR wax product is after refined, shaping, packaging.
2. in accordance with the method for claim 1, it is characterised in that the weight content of the n-alkane in the F-T synthetic products is more than 80%.
3. in accordance with the method for claim 1, it is characterised in that process（One）The operating condition of middle hydro-conversion is：The h of volume space velocity 0.2~2.0 when 3~10MPa of reaction pressure, 150~300 DEG C of reaction temperature, liquid-1With hydrogen to oil volume ratio 100~1000:1.
4. in accordance with the method for claim 1, it is characterised in that described catalyst is Ni/Al2O3、W-Ni/Al2O3、Mo-Ni/Al2O3Or W-Mo-Ni/Al2O3Catalyst, in catalyst active metal component with the weight content that oxide is counted be 20%~70%.
5. in accordance with the method for claim 1, it is characterised in that step（3）Solid mass is placed to apply the pressure of more than 0.5kPa to wax layer by wax layer surface in sweating effort.
6. in accordance with the method for claim 5, it is characterised in that described places solid mass in the following ways on wax layer surface：It is disposable in sweating effort to add the solid mass that produce more than 0.5kPa pressure.
7. in accordance with the method for claim 6, it is characterised in that disposable when sweating starts to add the solid mass that produce 1.4~20.0kPa pressure.
8. in accordance with the method for claim 5, it is characterised in that described places solid mass in the following ways on wax layer surface：Added several times in sweating effort, i.e., being added in every 0.1~20.0 h can produce the solid mass of more than 0.5kPa pressure.
9. in accordance with the method for claim 8, it is characterised in that being added in every 0.1~10.0 h can produce the solid mass of 1.4~10.0 kPa pressure.
10. in accordance with the method for claim 5, it is characterised in that described solid mass surfacing, overall dimensions are less than sweatbox inner wall size, and there is the hole for running through up and down inside.
11. in accordance with the method for claim 5, it is characterised in that the density of described solid mass is more than 4g/cm3。
12. in accordance with the method for claim 5, it is characterised in that described solid mass is that density is 6~12g/cm3, the material of solid mass is selected from zinc, iron, copper, lead and its alloy.
13. in accordance with the method for claim 1, it is characterised in that step（3）Described in the wax layer that forces air flow through use to increase above wax layer and air pressure and/or air pressure reduced below wax layer, wax layer upper and lower is formed pressure difference and realize, described pressure difference is 10~500 kPa.
14. in accordance with the method for claim 1, it is characterised in that step（2）Described in rate of temperature fall be 2.5 DEG C/h~3.5 DEG C/h.
15. in accordance with the method for claim 1, it is characterised in that step（2）Described in the predetermined temperature lowered the temperature for 10 DEG C~20 DEG C below raw material melt drop temperature.
16. in accordance with the method for claim 1, it is characterised in that step（3）Described in sweating effort heating rate be 2.0 DEG C/h~3.0 DEG C/h.
17. in accordance with the method for claim 1, it is characterised in that step（3）Described in constant temperature time be 0.1~5.0 hour.
18. in accordance with the method for claim 1, it is characterised in that step（3）Described in force air flow through wax layer sweating effort the intensification initial stage implement.
19. in accordance with the method for claim 11, it is characterised in that step（3）Described in force air flow through wax layer be utilized in wax layer top increase air pressure realize：Apply the gauge pressure pressure of 20~200 kPa above wax layer, and wax layer lower section remains normal pressure.
20. in accordance with the method for claim 11, it is characterised in that step（3）Described in force air flow through wax layer be utilized in wax layer lower section reduce air pressure realize：Air pressure keeps normal pressure above wax layer, and the gauge pressure pressure of -20~-80 kPa is maintained below wax layer.
21. in accordance with the method for claim 1, it is characterised in that described sweatbox is sweating ware.
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| CN110734784A (en) * | 2018-07-19 | 2020-01-31 | 内蒙古伊泰煤基新材料研究院有限公司 | synergistic wax for EVA hot melt adhesive and preparation method thereof |
| CN111088075A (en) * | 2018-10-23 | 2020-05-01 | 内蒙古伊泰煤基新材料研究院有限公司 | Method for preparing wax series products by using Fischer-Tropsch hydrogenation bottom-reducing oil |
| CN111205891A (en) * | 2018-11-21 | 2020-05-29 | 内蒙古伊泰煤基新材料研究院有限公司 | Wax for plastic processing and preparation method thereof |
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| CN103102971A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method for wax temperature-sensitive medium for temperature control valve |
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| GB687235A (en) * | 1950-03-24 | 1953-02-11 | Bataafsche Petroleum | Improvements in and relating to the treatment of paraffin wax |
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| CN110734784A (en) * | 2018-07-19 | 2020-01-31 | 内蒙古伊泰煤基新材料研究院有限公司 | synergistic wax for EVA hot melt adhesive and preparation method thereof |
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| CN111205891A (en) * | 2018-11-21 | 2020-05-29 | 内蒙古伊泰煤基新材料研究院有限公司 | Wax for plastic processing and preparation method thereof |
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| CN106883876B (en) | 2019-01-25 |
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