CN107523349B - A kind of sweating and the method for preparing explosive insensitiveness wax - Google Patents
A kind of sweating and the method for preparing explosive insensitiveness wax Download PDFInfo
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- CN107523349B CN107523349B CN201710444666.XA CN201710444666A CN107523349B CN 107523349 B CN107523349 B CN 107523349B CN 201710444666 A CN201710444666 A CN 201710444666A CN 107523349 B CN107523349 B CN 107523349B
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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
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/005—Desensitisers, phlegmatisers
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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
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1081—Alkanes
- C10G2300/1085—Solid paraffins
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- Oil, Petroleum & Natural Gas (AREA)
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- Processes Of Treating Macromolecular Substances (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a kind of sweating and the methods for preparing explosive insensitiveness wax.The method of the present invention is on the basis of common sweating process, oil soluble emulsifying agent and oil-soluble acid are dissolved in sweating raw material as oil phase material, using inorganic salt solution as water-phase material, sweating is carried out after emulsification, the bubble and salting liquid generated using oil-soluble acid and inorganic salt reaction forms short space after being discharged, the channel of discharge oil is formed in favor of the quick discharge of oil, the oil of liquid is carried out to force to separate wax and oil by wax layer using air-flow in sweating effort simultaneously, so that sweating de-oiling method be allow to produce the explosive insensitiveness wax product of low oil content.The method of the present invention has many advantages, such as that equipment investment is low, production process is simple and operating cost is low, safety, energy conservation and solvent-free pollution.
Description
Technical field
The invention belongs to Wax special production technical fields, more particularly to a kind of sweating and prepare the side of explosive insensitiveness wax
Method.
Background technique
Explosive is the substance that rapidly can be burnt or decompose, can be in very short time under certain outside energy effect
Interior vigorous combustion (exploding) generates a large amount of heat and gas, carries out stable detonation formula to the external world and does work.It is currently used
Explosive is TNT, high explosive heisuojin (RDX, three ammonium nitrate of ring cyclonite) and octogen (HMX, cyclotetramethyltetranitrosamine)
Deng.
Under given conditions, the safety that the various sensitivity of explosive and powder charge use has close relationship, certain
Various sensitivity are lower in range, and safety in utilization is better.It may be expressed as: heat sensitivity, flame according to different detonation momentum sensitivity
Sensitivity, mechanical sensitivity (including impact sensitivity, friction sensitivity), shock sensitivity, detonation sensitivity etc..
Some high explosives, such as RDX and HMX, explosion property very well or the performance with certain special requirement, only
It is that safety is poor, the requirement of high-power and high security cannot be met simultaneously, it is necessary to considers the different method of sensitivity
Give insensitiveness or insensitiveness processing.
Explosive phlegmatizer refers to the substance to reduce explosive sensitivity.The deterrent for being usually used in reducing explosive mechanical sensitivity has
Wax class, high polymer etc..Wax has at home and abroad continued to use over half a century as explosive phlegmatizer, its efficient insensitive action has been
Recognized by people.Explosive insensitiveness wax has highly important effect to the insensitiveness of explosive, be to ensure that explosive storage, transport,
In the entire life cycle used an important factor for safety.Some dedicated explosive insensitiveness waxes require fusing points 70 DEG C~80 DEG C it
Between, oil content less than 0.5%, without mechanical admixture.
The general name of the pertroleum wax all kinds of wax products obtained that are crude oil after refining processing from wax-containing distillate, including liquid
Body paraffin, soap manufacturing paraffin, paraffin and microwax.Paraffin be in crude oil lube cut through dewaxing, de-oiling, purification and molding
Production, typically contain C20~C50The components such as n-alkane, isoparaffin and a small amount of cycloalkane, usual fusing point is 50 DEG C~
74℃.Microwax be decompression residuum after propane equal solvent depitching again through dewaxing, de-oiling, purification and molding and etc. production
, generally by C30~C60Isoparaffin and a small amount of n-alkane, cycloalkane composition, usual dropping point be 65 DEG C~92 DEG C, Gu
There is the needle-like crystal structure more tiny than paraffin under state.Paraffin of the fusing point of domestic production at present between 70 DEG C~80 DEG C
Oil content usually between 0.8%~2.0%, the oil content of microwax of the fusing point between 70 DEG C~80 DEG C usually 1.5%~
Between 3.5%, it is not able to satisfy the requirement of certain special dynamite insensitiveness waxes.
In pertroleum wax production process, dewaxing is that the slack wax that oil content is 10~30% or so is prepared by raw material of crude oil fractions
Process.De-oiling is that the process of the base oil wax below of oil content 2% is prepared using slack wax as raw material, and de-oiling technique mainly has solvent
De-oiling and sweating de-oiling.Through clay-filtered or hydrofinishing and molding, packaging and other steps, commodity stone can be obtained again in base oil wax
Oily wax.
Solvent deoiling method is according to wax and oil in selective solvent (acetone, benzene and toluene mixture；Or acetone, toluene；
Or methyl ethyl ketone, toluene) in the property of different solubility separated.Solvent deoiling technique with production process, receive by continuous, wax
Rate is high, finished product wax oil content can very low, lower production costs the advantages that, be the mainstream of current large-scale production petroleum paraffin product
De-oiling technique.But solvent deoiling technique investment of production equipment is big；It needs largely to use solvent in production process, recycling design needs
Consume a large amount of energy；Contain benzene homologues in solvent, environment can be impacted；Solvent is inflammable, be easy to cause production accident.
Sweating de-oiling method is separated using wax and oil property with different melting points.Point of various components in pertroleum wax
Son amount Bu Tong can all make its fusing point different with structure.When being all n-alkane structure, the biggish n-alkane of molecular weight melts
Point is higher, and the fusing point of the lesser n-alkane of molecular weight is lower；When molecular weight is identical, the fusing point of isoparaffin and cycloalkane is wanted
Lower than n-alkane, and isomery degree more high-melting-point is lower, or even is at normal temperature just in liquid condition, i.e., usually said
Oil.Sweating de-oiling method does not use solvent in process of production, thus sweating method safety, energy conservation and on environment without influence.
Common sweating de-oiling technique mainly comprises the steps that (1) preparation: pad water is (with water full of sweatbox
Ware plate lower space) charge (raw material is heated to being packed into sweatbox when fusing point or more is in a liquid state) afterwards；(2) crystallize: by raw material with
Rate of temperature fall no more than 4 DEG C/h progressively cools to 10 DEG C~20 DEG C of its fusing point or less.In cooling procedure, various components are by molten
The sequence of point from high to low, which successively crystallizes, forms solid；(3) sweating: when wax layer temperature reach preset cooling final temperature it
Afterwards, pad water is bled off；Raw material is slowly heated to preset sweating final temperature again.In sweating effort, various components are by molten
The sequence of point from low to high is successively fused into liquid and flows out (under wax), and the wax layer residue (on wax) finally obtained is exactly Gao Rong
The wax of point, low oil-containing；(4) it refines: collecting crude product and (continue to increase temperature after sweating effort, be taken out on wax with fusing, i.e.,
For crude product), through clay-filtered (it be warming up to predetermined temperature after melting crude product, carclazyte is added and constant temperature is stirred to pre- timing
Between after filtering) after, reshaping, packaging i.e. be purpose product.
Common sweating separating technology can produce fusing point has coarse flaky crystal structure under 40 DEG C~60 DEG C of solid-state
Soap manufacturing paraffin and low melt point paraffin, be not suitable for producing explosive insensitiveness wax product of the fusing point at 70 DEG C~80 DEG C.Have experiments have shown that, it is general
Logical sweating de-oiling technique production fusing point is in 70 DEG C or so of high melting point oil wax product, even if using sweating sessions (drop is extended
Low heating rate) and the method that improves sweating final temperature, the oil content on sweating later period wax is unrelated with yield, i.e. containing on wax
Oil mass does not decline with the decline of yield, so common sweating de-oiling technique is not suitable for producing explosive of the fusing point at 70 DEG C~80 DEG C
Insensitiveness wax product, especially oil-containing figureofmerit cannot meet technical requirement.
Compared with solvent deoiling, sweating de-oiling technique is intermittently operated, and product yield is lower, the production cycle is longer, but
Be sweating de-oiling technique have small investment, production process is simple, operating cost is low, production process is safe, it is energy saving and to environment without
The advantages that pollution, still has part of the manufacturer producing soap manufacturing paraffin product using this method at present.
For many years, sweating method has obtained some development in production equipment and process aspect, such as CN89214332(vertical type square
Shape multipul sections spacer diaphoresis tank), CN94223980.6(ware type sudorific device), CN98233254.8(Paraffin sweating pot),
CN200920033500.X(novel paraffin sweating tank), a kind of Efficient paraffin sweatbox of CN201210508905.0(),
CN201320127680.4(tubular type paraffin deoiler) etc., it is improved in sweating de-oiling production equipment；CN91206202
(a kind of high-efficient sweat pot for paraffin wax) improves in sweating de-oiling technique.But these methods cannot still produce fusing point 70 DEG C~
80 DEG C of explosive insensitiveness wax product.
Sweating de-oiling technique is the unique solvent-free de-oiling method being currently known for commercial scale petroleum paraffin product,
In the today for advocating green low-carbon, environmental protection and energy saving, the demand using sweating de-oiling technique production explosive insensitiveness wax is more urgent.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of sweating and the methods for preparing explosive insensitiveness wax.Specifically
Say it is that oil soluble emulsifying agent and oil-soluble acid are preferably dissolved on the basis of common sweating process by sweating using sweatbox
Raw material carries out sweating after emulsification, utilizes oil-soluble acid and inorganic salts as oil phase material using inorganic salt solution as water-phase material
It reacts the bubble generated and forms short space after salting liquid discharge, be conducive to the discharge of sweating stage liquid oil；It is sending out simultaneously
Air-flow is utilized, to force separation wax and oil, to enhance separating effect by wax layer and accelerate separating rate during sweat；And increase
The constant temperature stage for adding crystallization and sweating effort allows this solvent-free de-oiling method of sweating to prepare explosive insensitiveness wax product.This
Inventive method has many advantages, such as that equipment investment is low, production process is simple and operating cost is low, energy-saving safe and solvent-free pollution.
A kind of sweating of the invention and the method for preparing explosive insensitiveness wax, including the following contents:
A: emulsification
(A1) prepared by oil phase material: using fusing point be 60 DEG C~74 DEG C, paraffin of the oil content no more than 2.0 mass % is sweating
Raw material is added oil soluble emulsifying agent and oil-soluble acid after heating fusing, stirs evenly, forms oil phase material；
(A2) prepared by water-phase material: inorganic salts being dissolved in water, after heating, form water-phase material；
(A3) prepared by emulsion: the oil phase material that (A1) is obtained is added in the water-phase material that (A2) is obtained under agitation
In, continue stirring 5~60 minutes, to form emulsion；
B: sweating
(B1) emulsion of (A3) process preparation preparation: is packed into sweatbox；
(B2) crystallize: first with 2.0 DEG C/h~40.0 DEG C/h rate by emulsion be cooled to+4 DEG C of sweating raw material fusing point~
+ 15 DEG C of fusing point, then wax layer is cooled to by proper temperature with 1.0 DEG C/h~3.0 DEG C/h rate, high temperature constant temperature is for a period of time；Again
5 DEG C~20 DEG C of sweating raw material fusing point or less of predetermined temperature is cooled to 0.5 DEG C/h~2.5 DEG C/h rate；
(B3) sweating: with the heating of 0.5 DEG C/h~2.5 DEG C/h rate；Wax layer reaches predetermined temperature and constant temperature for a period of time
After stop sweating；Wax layer is forced air flow through in sweating effort；
(B4) it refines: being explosive insensitiveness wax product after refining on wax.
In method of the invention, the oil content (in mass) of the sweating raw material paraffin is less than 2.0%；Fusing point is general
It is 60 DEG C~74 DEG C, preferably 64 DEG C~70 DEG C.
In method of the invention, sweating raw material is emulsified in the presence of oil soluble emulsifying agent and oil-soluble acid with water-phase material
After carry out sweating.Oil soluble emulsifying agent described in step (A1) is selected from nonionic surface active agent, anionic surface activity
One or more of agent, cationic surface active agent, amphoteric surfactant.The HLB value of oil soluble emulsifying agent be 1~
10, preferably 3~8；The freezing point or fusing point of surfactant are lower than the maximum temperature of step (B3) sweating (i.e. in step (B3)
The predetermined temperature).The oil soluble emulsifying agent is preferably the compound emulsifying agent that two or more surfactants is constituted.
Wherein, it is stearic to be selected from sorbitan monooleate, anhydrous sorbitol list for the nonionic surface active agent
Acid esters, diethylene glycol aliphatic ester, diethylene glycol monolaurate, sorbitan monopalmitate, tetraethylene glycol list are stearic
One group of substance that acid esters, polyoxypropylene stearate, sorbitan mono-laurate, polyoxyethylene fatty acid ester are constituted；Yin
Ionic surfactant is selected from fatty alcohol sulfate monoethanolamine salt, pareth sulfate, oleamide yl carboxylic acid
Sodium, sodium alkyl benzene sulfonate, N- methyl oleoyl taurate, sodium butylnaphthalenesulfonate, Disodium sulfosuccinate, suitable succinate monoester
One group of substance that sodium sulfonate is constituted.The cationic surface active agent is selected from benzyl quaternary ammonium salt, dodecyl dimethyl benzyl
Ammonium chloride, dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyltrimethylammonium chloride, three second
One group of substance that amide oleate is constituted；Amphoteric surfactant is selected from empgen BB, dodecyl dimethyl oxygen
Change ammonium, aliphatic group imidazolidine derivatives, alkyl imidazoline derivatives, derivative of fatty acid, amphoteric modified epoxy ethane to add
The one group of substance constituted at object.
In method of the invention, oil-soluble acid described in step (A1) is soluble in sweating raw material and can be with step (A2) institute
The inorganic salt reaction stated generates the organic acid of gas.Organic acid is selected from positive tenth of the twelve Earthly Branches acid, n-capric acid, positive undecanoic acid, lauric acid, positive 13
Acid, myristic acid, positive pentadecanoic acid, palmitinic acid, pearly-lustre resin acid, stearic acid, positive nonadecanoic acid, arachidic acid, positive heneicosoic acid, behenyl
Sour, positive tricosanic acid, lignoceric acid, positive neocerotic acid, cerinic acid, positive carboceric acid, montanic acid, positive motanic acid, melissic acid, positive three
One group of substance that undecanoic acid, lacceroic acid, leaf lice acid, linoleic acid, palmitoleic acid, oleic acid, erucic acid, selacholeic acid are constituted.Preferably
No special odor, nonhazardous, be easy to get and price is low, fusing point lower than sweating heating maximum temperature organic acid, including linoleic acid,
Palmitoleic acid, oleic acid, erucic acid, selacholeic acid, n-capric acid, positive undecanoic acid, lauric acid, positive tridecanoic acid, myristic acid, positive pentadecanoic acid,
One group of substance that palmitinic acid, pearly-lustre resin acid are constituted.
In method of the invention, inorganic salts described in step (A2) are can to react with oil-soluble acid described in step (A1)
The water-soluble inorganic salt of gas is generated, one or more of carbonate, bicarbonate, sulphite, bisulfites are selected from,
The carbonic acid such as preferably cheap, from a wealth of sources, itself and reaction product are nontoxic, the sodium carbonate, the potassium carbonate that have no irritating odor
One of salt and its bicarbonates such as mixture and/or sodium bicarbonate, saleratus one of and its mixture institute structure
At one group of substance.The concentration (quality %, similarly hereinafter) of the inorganic salt solution be 0.1%~10.0%, preferably 0.5%~
5.0%。
In method of the invention, the composition of emulsion obtained by step (A3) are as follows: sweating raw material 55.0%~90.0%, water phase
Material 9.8%~29.0%, oil soluble emulsifying agent 0.1%~6.0%, oil-soluble acid 0.1%~10.0%.It is preferred that are as follows: sweating raw material
66.0%~83.0%, water-phase material 15.0%~25.0%, oil soluble emulsifying agent 1.8%~4.0%, oil-soluble acid 0.2%~5.0%.
The emulsification uses the routine operation of this field.The condition of emulsification is general are as follows: at 70 DEG C~98 DEG C, with 50~
5000 revs/min of mixing speed mixes 5~60 minutes；Preferably at 75 DEG C~95 DEG C, with 100~1000 revs/min
Mixing speed mixes 10~30 minutes.
It is preferred during step (B2) that hair is first cooled to 4.0 DEG C/h~30.0 DEG C/h rate in method of the invention
Within the scope of+10 DEG C of+4 DEG C~fusing point of sweat raw material fusing point, thereafter the preferably 1.5 DEG C/h of the rate of temperature fall before high-temperature constant temperature section~
2.5℃/h.The proper temperature of the high-temperature constant temperature section of the temperature-fall period is sweating raw material fusing point~+4.0 DEG C of fusing point.It is cooled
The time of the high-temperature constant temperature section of journey is 0.1~6.0 hour, preferably 0.5~5.0 hour, more preferably 1.0~4.0 hours.
In method of the invention, rate of temperature fall of the temperature-fall period of step (B2) crystallization after high-temperature constant temperature section is excellent
Select 1.0 DEG C/h~2.0 DEG C/h.The cooling final temperature is preferably 8 DEG C~15 DEG C of sweating raw material fusing point or less.
In method of the invention, the sweatbox is sweating ware, and wax layer pressurizing device added above and/or
Increase vacuum plant below wax layer, to make wax layer form pressure difference up and down during step (B3).The pressure air-flow
It is used by wax layer and increases pressure (air pressure) above wax layer and/or reduce pressure (air pressure) below wax layer, keep wax layer upper and lower
Side (side) forms pressure difference and realizes.The pressure difference is generally 0.1~5.0 atmospheric pressure, preferably 0.2~2.0 atmosphere
Pressure, to force air flow through wax layer.
In method of the invention, the preferably 1.0 DEG C/h~2.0 DEG C/h of heating rate described in step (B3).The heating
Predetermined temperature (i.e. final temperature) be -1 DEG C of fusing point of -10 DEG C~purpose product of purpose product fusing point.Described being warming up to is predetermined
After temperature, the increase constant temperature stage can be such that wax separates with oil more sufficiently, and the time in constant temperature stage is 0.1~10.0 hour, preferably
It is 1.0~8.0 hours, most preferably 2.0~5.0 hours.
In method of the invention, the heating rate and cooling rate of said wax layer can pass through air bath, water-bath, oil bath
Or other feasible modes are controlled, it is preferred to use water-bath or oil bath.Wax layer heating is controlled using water-bath or oil bath mode
When rate and rate of temperature fall, collet can be increased outside sweating ware, collet is connected with removable coil pipe and the circulatory system, the circulatory system
With program cooling/heating function, the substances such as water or conduction oil are added as circulatory mediator in the circulatory system；Coil pipe is soaked after charging
Not and be fixed in wax layer, can make wax layer lifting/lowering temperature process faster, wax layer more uniform temperature.
In method of the invention, wax layer is forced air flow through described in step (B3) can be real in sweating effort any stage
It applies, preferably implements at sweating initial stage.
In method of the invention, wax layer is forced air flow through described in step (B3) and is utilized in increase air pressure above wax layer
It realizes, can such as apply the gauge of 0.2~2.0 atmospheric pressure above wax layer, and remain normal pressure below wax layer.
In method of the invention, wax layer is forced air flow through described in step (B3) and is utilized in reduction air pressure below wax layer
It realizes, normal pressure can be such as kept above wax layer, and maintain the gauge of -0.2~-0.8 atmospheric pressure below wax layer.
Sweating de-oiling method is to be separated using wax and oil property with different melting points to produce pertroleum wax, for petroleum
Wax sweating process studies have shown that oil is gradually discharged along crystalline portion in sweating effort, be similar to liquid in capillary
The case where middle flowing.But the high melting point oil wax product for fusing point at 70 DEG C or so, due to isoparaffin and ring in raw material
The substances such as alkane increase, and chemical composition is complicated, cause crystals upon crystallization structure more fine and compact, are formed to the discharge of oil huge
Filter flow resistance power, this result in only by gravity natural separation common sweating effort in wax be difficult to be kept completely separate with oil.Therefore general
Logical sweating de-oiling technique cannot produce fusing point in the explosive insensitiveness wax product of 70 DEG C~80 DEG C, oil content less than 0.5%.
The present invention produces to make the method for this solvent-free production pertroleum wax of sweating de-oiling be suitable for preparing explosive insensitiveness wax
Product are difficult to separate reason with oil for wax by the further investigation to common sweating effort, by using gas in sweating effort
Stream forces oil to enhance separating effect with the separation of wax and accelerate separating rate by the method that wax layer carries out fluid oil.
Increasing the high temperature constant temperature stage in crystallization process can make the crystallization of pertroleum wax bigger, be conducive to discharge oily in sweating effort.
For pertroleum wax crystallization process studies have shown that the chemical composition of pertroleum wax is to determine the main factor of crystal habit, simultaneously
The condition of cooling procedure also will affect crystal habit, especially near fusing point at a temperature of cooling condition to crystal habit
It influences most obvious.When being cooled near fusing point, the n-alkane of larger molecular weight has formed crystallization and has been precipitated pertroleum wax, this part
Crystalline solid can be used as the nucleus for being subsequently formed crystallization, increases the high temperature constant temperature stage at this time, nucleus can be enable sufficiently to increase,
Larger sized crystal is formed, it is this although this larger sized crystal is coarse not as good as the crystallization of low melt point paraffin
The crystal structure of increase is also highly beneficial to sweating stage discharge oil.Sweating raw material is further preferably mixed into oil-soluble acid and oil
Soluble emulsification agent carries out sweating after w/o type emulsion is made with inorganic salt solution again, and inorganic salt solution is in emulsion with small grain
Sub- form is evenly distributed in raw material wax layer；Since the acidity of selected oil-soluble acid is weaker and is respectively at oil with inorganic salts
Mutually and in water phase, generates the reaction of gas and carried out with slower speed；Sweating raw material arrives sweating effort after being cooled to fusing point or less
Wax layer is in softer solid state in the time of termination, during this oil-soluble acid and inorganic salts gradually occurs to chemically react and
Gas is released, forms equally distributed micro-bubble in raw material wax layer；Using air-flow by wax layer in sweating effort, one
Aspect can carry out inorganic salt solution to form short space in wax layer, and the space that these short spaces and bubble generate is being sent out
It is easy to be formed several tiny channels in wax layer during sweat, is conducive to discharge oily in sweating effort；On the other hand it carries
The oil of liquid is out to force separation wax and oil, to enhance separating effect and accelerate separating rate.Selected oil-soluble acid and
The fusing point of surfactant is lower than the maximum temperature of sweating effort, and all belongs to polar molecule, poor with the intermiscibility of sweating raw material,
It can be discharged in sweating effort with fluid oil.The constant temperature stage for being aided with sweating effort again makes wax separate more abundant grade side with oil
Method significantly reduces the oil content of product, and sweating de-oiling technique is allow to produce explosive insensitiveness wax product.
This have the advantage that: the method by using air-flow to carry out fluid oil by wax layer in sweating effort
The separation for forcing wax and oil, enhances separating effect and accelerates separating rate；Crystalline size is increased using high temperature crystallization, simultaneously
Short space is generated after generating the space and inorganic salt solution discharge that micro-bubble is formed using oil-soluble acid and inorganic salt reaction
Several tiny channels are formed, the quick discharge of oil is also beneficial to；And the processes such as constant temperature stage for increasing sweating effort, to make
Sweating de-oiling technique can prepare explosive insensitiveness wax product, and have plant investment is low, production process is simple and operating cost is low,
The advantages that safety, energy conservation and solvent-free pollution environment.
Specific embodiment
The present invention is sweating raw material by selecting suitable common paraffin, on the basis of common sweating process, sweating ware
Top connects dismountable sealing device and connect with pressurized buffer tank and compressor, and/or connects and depressurize in sweating ware lower part
Surge tank and vacuum pump；Oil-soluble acid and emulsifier are melted and are preferably added in the heating of sweating raw material, after inorganic salt solution emulsification
It is packed into sweating ware；Wax layer heating-cooling speed is controlled with water-bath；Wax layer temperature is down to sweating raw material melting temperature nearby and high-temperature constant
Warm a period of time；Continue to be cooled to preset temperature；In sweating effort, start compressor in wax layer positive pressure formed above, and/
Or starting vacuum pump is in wax layer negative pressure formed below, to force air flow through wax layer；Wax layer temperature reaches preset temperature simultaneously
Constant temperature stops sweating effort afterwards for a period of time；It is explosive insensitiveness wax product after refining on wax.
The method that 1-4 illustrates sweating of the invention and prepares explosive insensitiveness wax by the following examples.As without especially
It indicates, being related to % below is mass percent, and the pressure is gauge pressure.
Embodiment 1
The present embodiment includes: A: emulsification and B: sweating two parts.
A: emulsification
This part includes the preparation of (A1) oil phase material, the preparation of (A2) water-phase material, (A3) emulsion three steps of preparation.
(A1) prepared by oil phase material: taking 66#Scale wax (Sinopec Gaoqiao Petrochemical Company, 66.60 DEG C of fusing point, oil content
1.64%) 2.6Kg diethylene glycol aliphatic ester, 0.8Kg anhydrous sorbitol list palm is added after being heated to 76 DEG C of fusings in 70.0Kg
The positive pentadecanoic acid of acid esters, 0.4Kg empgen BB and 2.5Kg, stirs evenly.
(A2) prepared by water-phase material: the Na that compound concentration is 2.3%2CO3Solution takes 23.7Kg and is heated to 80 DEG C；
(A3) prepared by emulsion: with the oil phase material of 300 revs/min of speed stirring (A1) process preparation, and by (A2)
The water-phase material of process preparation is added in oil phase material, is continued to stir 30min, is formed water-in-oil type emulsion.
B: sweating
This part includes (B1) preparation, (B2) cooling-high temperature constant temperature-decrease temperature crystalline (B3) heating-constant temperature hair
Sweat, (B4) refine four steps.
(B1) preparation
The sealing system of sweating ware and pressurized buffer tank and compressor are connected；Pressure-reducing cushioning is installed in sweating ware lower part
Tank simultaneously connects vacuum pump；Sweating ware collet and removable coil pipe are connect with the circulatory system, coil pipe is fixed on sweating ware；With
Water is heat medium；The heating function for starting the circulatory system, makes recirculated water be warming up to 72 DEG C.Water is padded below sweating ware ware plate.It will
(A3) sweating ware is added in the emulsion of process preparation.The sealing system of sweating ware is installed.
(B2) cooling-high temperature constant temperature-decrease temperature crystalline
Emulsion stands the refrigerating function of the starting circulatory system after 1.0h, controls wax layer temperature with the cooling speed of 2.0 DEG C/h
Rate makes wax layer temperature drop to 68.0 DEG C and 2.5 hours progress high temperature constant temperatures of constant temperature, so that crystal sufficiently increases；Again with 1.5 DEG C/
The rate of temperature fall of h makes wax layer temperature drop to 56.0 DEG C so that wax layer crystallizes to form solid.
(B3) heating-constant temperature sweating
Sweating ware is discharged and pads water.Sweating ware outlet connection intermediate storage tank (I) is to receive under wax；Start compressor and keeps adding
Pressure buffering pressure inside the tank is stablized keeps normal pressure below 1.3~1.5 atmospheric pressure, sweating ware ware plate；Start circulation system
Function makes wax layer temperature be increased to 64.0 DEG C with the heating rate of 1.5 DEG C/h.Stop compressor.
It opens vacuum pump and pressure-reducing cushioning pressure inside the tank is kept to stablize the air pressure above -0.4~-0.6 atmospheric pressure, wax layer
Keep normal pressure；Wax layer temperature is set to be increased to 66.5 DEG C and constant temperature 4.0 hours with the heating rate of 1.0 DEG C/h, so that in wax layer
Wax is sufficiently separated with oil.Stop vacuum pump, terminates sweating degreasing process.
Sweating ware exports changing-over crude product storage tank (I) to receive on wax；Continue the temperature of raising recirculated water to 90 DEG C, with molten
Change and take out on wax, as crude product (I).
(B4) it refines
Crude product (I) is explosive insensitiveness wax product (I) after clay-filtered.
Explosive insensitiveness wax product (I) property: 70.8 DEG C of fusing point；Oil content 0.41%；Mechanical admixture, nothing.Meet explosive insensitiveness
The associated specifications of wax product.The yield of explosive insensitiveness wax product (I) is 23.8%(relative to raw material 66#Scale wax).
Embodiment 2
The present embodiment includes: A: emulsification and B: sweating two parts.
A: emulsification
This part includes the preparation of (A1) oil phase material, the preparation of (A2) water-phase material, (A3) emulsion three steps of preparation.
(A1) prepared by oil phase material: taking 66#Scale wax (with embodiment 1) 79.0Kg is added after being heated to 84 DEG C of fusings
1.7Kg sorbitan monostearate, 0.4Kg diethylene glycol monolaurate, 0.5Kg polyoxyethylene fatty acid ester and
The palmitoleic acid of 1.5Kg, stirs evenly.
(A2) prepared by water-phase material: the NaHCO that compound concentration is 3.0%3Solution takes 16.9Kg and is heated to 90 DEG C；
(A3) prepared by emulsion: with the oil phase material of 650 revs/min of speed stirring (A1) process preparation, and by (A2)
The water-phase material of process preparation is added in oil phase material, is continued to stir 20min, is formed water-in-oil type emulsion.
B: sweating
With embodiment 1.
Explosive insensitiveness wax product (II) property manufactured in the present embodiment: 70.6 DEG C of fusing point；Oil content 0.38%；Mechanical admixture,
Nothing.Meet the associated specifications of explosive insensitiveness wax product.The yield of explosive insensitiveness wax product (II) is 24.7%(relative to original
Material 66#Scale wax).
Embodiment 3
The present embodiment includes: A: emulsification and B: sweating two parts.
A: emulsification
This part includes the preparation of (A1) oil phase material, the preparation of (A2) water-phase material, (A3) emulsion three steps of preparation.
(A1) prepared by oil phase material: taking 66#Scale wax (with embodiment 1) 82.0Kg is added after being heated to 88 DEG C of fusings
1.3Kg sorbitan monostearate, 0.5Kg sorbitan mono-laurate, 0.2Kg polyoxyethylene fatty acid ester and
The positive undecanoic acid of 1.0Kg, stirs evenly.
(A2) prepared by water-phase material: the K that compound concentration is 2.5%2CO3Solution takes 15.0Kg and is heated to 95 DEG C；
(A3) prepared by emulsion: with the oil phase material of 1000 revs/min of speed stirring (A1) process preparation, and by (A2)
The water-phase material of process preparation is added in oil phase material, is continued to stir 15min, is formed water-in-oil type emulsion.
B: sweating
With embodiment 1.
Explosive insensitiveness wax product (III) property manufactured in the present embodiment: 70.3 DEG C of fusing point；Oil content 0.40%；Mechanical admixture,
Nothing.Meet the associated specifications of explosive insensitiveness wax product.The yield of explosive insensitiveness wax product (III) is 24.5%(relative to original
Material 66#Scale wax).
Embodiment 4
The present embodiment includes: A: emulsification and B: sweating two parts.
A: emulsification
This part includes the preparation of (A1) oil phase material, the preparation of (A2) water-phase material, (A3) emulsion three steps of preparation.
(A1) prepared by oil phase material: taking 66#Scale wax (with embodiment 1) 75.0Kg is added after being heated to 80 DEG C of fusings
2.4Kg diethylene glycol monolaurate, 0.5Kg sorbitan monooleate, 0.3Kg triacetamide oleate and 2.0Kg
Linoleic acid stirs evenly.
(A2) prepared by water-phase material: the KHCO that compound concentration is 3.6%3Solution takes 19.8Kg and is heated to 85 DEG C；
(A3) prepared by emulsion: with the oil phase material of 450 revs/min of speed stirring (A1) process preparation, and by (A2)
The water-phase material of process preparation is added in oil phase material, is continued to stir 30min, is formed water-in-oil type emulsion.
B: sweating
With embodiment 1.
Explosive insensitiveness wax product (IV) property manufactured in the present embodiment: 71.0 DEG C of fusing point；Oil content 0.43%；Mechanical admixture,
Nothing.Meet the associated specifications of explosive insensitiveness wax product.The yield of explosive insensitiveness wax product (IV) is 23.6%(relative to original
Material 66#Scale wax).
The method that can be seen that sweating of the invention by embodiment 1-4 and prepare explosive insensitiveness wax passes through and increases pressurization
And/or the improvement to sweatbox such as vacuum facility；By the way that sweating raw material is mixed into oil-soluble acid and is generated with inorganic salt reaction
Gas form the short space formed after micro-bubble and salting liquid discharge in wax layer, force air-flow logical in sweating effort
Cross the improvement to sweating process such as wax layer, the constant temperature stage for increasing crystallization and sweating effort；Enhance the separating effect of wax and oil
And accelerate separating rate, thus allow sweating de-oiling technique prepare fusing point between 70 DEG C~80 DEG C, oil content is less than
0.5%, the explosive insensitiveness wax product without mechanical admixture.
Claims (20)
1. a kind of sweating and the method for preparing explosive insensitiveness wax, including the following contents:
A: emulsification
(A1) oil phase material prepare: using fusing point be 60 DEG C~74 DEG C, oil content no more than 2.0 mass % paraffin as sweating raw material,
Oil soluble emulsifying agent and oil-soluble acid is added after heating fusing, stirs evenly, forms oil phase material；
(A2) prepared by water-phase material: inorganic salts being dissolved in water, form water-phase material；
(A3) prepared by emulsion: the water-phase material that (A2) is obtained is added in the oil phase material that (A1) is obtained under agitation,
Continue stirring 5~60 minutes, to form emulsion；
B: sweating
(B1) emulsion of (A3) process preparation preparation: is packed into sweatbox；
(B2) it crystallizes: emulsion is cooled to by sweating raw material+4 DEG C~fusing point+15 of fusing point with 2.0 DEG C/h~40.0 DEG C/h rate
DEG C, then wax layer is cooled to by proper temperature with 1.0 DEG C/h~3.0 DEG C/h rate, high temperature constant temperature is for a period of time；Again with 0.5 DEG C/
H~2.5 DEG C/h rate is cooled to 5 DEG C~20 DEG C of sweating raw material fusing point or less of predetermined temperature；The proper temperature is sweating
Raw material fusing point~+4.0 DEG C of fusing point；
(B3) sweating: with the heating of 0.5 DEG C/h~2.5 DEG C/h rate；Wax layer reaches predetermined temperature and constant temperature stops afterwards for a period of time
Only sweating；Wax layer is forced air flow through in sweating effort；The predetermined temperature is purpose product fusing point -10 DEG C~purpose product
- 1 DEG C of fusing point；
(B4) it refines: being explosive insensitiveness wax product after refining on wax；
Wherein, the oil-soluble acid is selected from positive tenth of the twelve Earthly Branches acid, n-capric acid, positive undecanoic acid, lauric acid, positive tridecanoic acid, myristic acid, positive ten
Five acid, palmitinic acid, pearly-lustre resin acid, stearic acid, positive nonadecanoic acid, arachidic acid, positive heneicosoic acid, behenic acid, positive tricosanic acid, haze tallow
Sour, positive neocerotic acid, cerinic acid, positive carboceric acid, montanic acid, positive motanic acid, melissic acid, positive myricinic acid, lacceroic acid, leaf
At least one of one group of substance that lice acid, linoleic acid, palmitoleic acid, oleic acid, erucic acid, selacholeic acid are constituted；The inorganic salts choosing
From at least one of carbonate, bicarbonate, sulphite, bisulfites, metal sulfide.
2. according to the method for claim 1, which is characterized in that oil soluble emulsifying agent described in step (A1) is selected from nonionic
Type surfactant, anionic surfactant, cationic surface active agent, amphoteric surfactant constitute one group
Substance, the HLB value of oil soluble emulsifying agent are 1~10, and the freezing point or fusing point of oil soluble emulsifying agent are lower than step (B3) sweating
Maximum temperature.
3. according to the method for claim 2, which is characterized in that the nonionic surface active agent is selected from Sorbitan
Alcohol monoleate, sorbitan monostearate, diethylene glycol aliphatic ester, sorbitan monopalmitate, tetrem two
Alcohol monostearate, polyoxypropylene stearate, sorbitan mono-laurate, polyoxyethylene fatty acid ester constitute one group
Substance；The anionic surfactant be selected from fatty alcohol sulfate monoethanolamine salt, pareth sulfate,
Oleamide yl carboxylic acid sodium, sodium alkyl benzene sulfonate, N- methyl oleoyl taurate, sodium butylnaphthalenesulfonate, Disodium sulfosuccinate,
The one group of substance constituted along succinate monoester sodium sulfonate；The cationic surface active agent is selected from benzyl quaternary ammonium salt, 12
Zephiran, dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethyl
One group of substance that ammonium chloride, triacetamide oleate are constituted；The amphoteric surfactant be selected from empgen BB,
Dodecyldimethyl ammonium oxide, aliphatic group imidazolidine derivatives, derivative of fatty acid, amphoteric modified epoxy ethane addition
One group of substance that object is constituted.
4. according to the method for claim 2, which is characterized in that the oil soluble emulsifying agent is two or more surface-actives
The compound emulsifying agent that agent is constituted.
5. according to the method for claim 1, which is characterized in that oil-soluble acid described in step (A1) is soluble in sweating original
Expect and can generate with the inorganic salt reaction described in (A2) organic acid of gas.
6. according to the method for claim 1, which is characterized in that the oil-soluble acid is selected from linoleic acid, palmitoleic acid, oil
Acid, erucic acid, selacholeic acid, n-capric acid, positive undecanoic acid, lauric acid, positive tridecanoic acid, myristic acid, positive pentadecanoic acid, palmitinic acid, pearly-lustre
At least one of resin acid.
7. according to the method for claim 1, which is characterized in that the inorganic salts are selected from sodium carbonate, potassium carbonate, bicarbonate
At least one of sodium, saleratus.
8. according to the method for claim 1, which is characterized in that the mass concentration of inorganic salts is in the water-phase material
0.1%~10.0%.
9. according to the method for claim 1, which is characterized in that mixing speed described in step (A3) is 50~5000
Rev/min, the temperature for preparing emulsion is 70 DEG C~98 DEG C.
10. according to the method for claim 1, which is characterized in that the composition for the emulsion that step (A3) obtains are as follows: sweating is former
Expect that mass percent is 55.0%~90.0%, the mass percent of water-phase material is 9.8%~29.0%, the matter of oil soluble emulsifying agent
Measuring percentage is 0.1%~6.0%, and the mass percent of oil-soluble acid is 0.1%~10.0%.
11. according to the method for claim 10, which is characterized in that the composition for the emulsion that step (A3) obtains are as follows: sweating
Material quality percentage is 66.0%~83.0%, and the mass percent of water-phase material is 15.0%~25.0%, oil soluble emulsifying agent
Mass percent be 1.8%~4.0%, the mass percent of oil-soluble acid is 0.2%~5.0%.
12. according to the method for claim 1, which is characterized in that the time of high temperature constant temperature described in step (B2) be 0.1~
6.0 hour.
13. according to the method for claim 1, which is characterized in that the predetermined temperature of cooling described in step (B2) is sweating
8 DEG C~15 DEG C below raw material fusing point.
14. according to the method for claim 1, which is characterized in that force air flow through wax layer described in step (B3) and adopt
Increase air pressure above wax layer and/or reduce air pressure below wax layer, so that wax layer upper and lower is formed pressure difference and realize, it is described
Pressure difference is 0.1~5.0 atmospheric pressure.
15. according to the method for claim 1, which is characterized in that the time of constant temperature described in step (B3) is 0.1~10.0
Hour.
16. according to the method for claim 1, which is characterized in that force air flow through wax layer described in step (B3) and exist
Sweating initial stage implements.
17. according to the method for claim 14, which is characterized in that the wax layer that forces air flow through uses in wax layer
Fang Zengjia air pressure is realized, applies the gauge of 0.2~2.0 atmospheric pressure above wax layer, and remains normal pressure below wax layer.
18. according to the method for claim 14, which is characterized in that the wax layer that forces air flow through uses under wax layer
Side reduces air pressure and realizes, air pressure keeps normal pressure above wax layer, and the table of -0.2~-0.8 atmospheric pressure is maintained below wax layer
Pressure pressure.
19. according to the method for claim 1, which is characterized in that the sweatbox is sweating ware.
20. according to the method for claim 14, which is characterized in that the pressure difference is 0.2~2.0 atmospheric pressure.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015357A (en) * | 1988-01-04 | 1991-05-14 | Amoco Corporation | Wax sweating |
| CN1218094A (en) * | 1998-09-14 | 1999-06-02 | 薛世峰 | Preparation of fundamental oil of lubricant oil |
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2017
- 2017-06-13 CN CN201710444666.XA patent/CN107523349B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015357A (en) * | 1988-01-04 | 1991-05-14 | Amoco Corporation | Wax sweating |
| CN1218094A (en) * | 1998-09-14 | 1999-06-02 | 薛世峰 | Preparation of fundamental oil of lubricant oil |
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