CN107513424B - The production method of microwax - Google Patents

Abstract

The invention discloses a kind of production methods of microwax.This method is on the basis of common sweating de-oiling technique, the oil of liquid is carried out to force separation wax and oil by wax layer using air-flow in sweating effort, and preferably raw material and water or salting liquid are emulsified, it is also beneficial to the quick discharge of oil, so that sweating de-oiling method be allow to produce crystallite wax product.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

The production method of microwax

Technical field

The invention belongs to pertroleum wax production technical fields, more particularly to a kind of production method of microwax.

Background technique

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.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.Usually The dropping point of microwax is 65 DEG C~92 DEG C, has the needle-like crystal structure more tiny than soap manufacturing paraffin and paraffin under solid-state.

Dewaxing is that the process for the slack wax that oil content is 10~30% or so is prepared by raw material of lube cut.De-oiling be with Slack wax is the process that raw material prepares the scale wax below of oil content 2%, and de-oiling technique mainly has solvent deoiling and sweating de-oiling.Slightly Through clay-filtered or hydrofinishing and molding, packaging and other steps, commodity oil wax can be obtained again in 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 hydro carbons 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, and only need for raw material to be heated in production process fusing point with On temperature.

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 10~20 DEG C of its fusing point or less.In cooling procedure, various components press fusing point Sequence from high to low successively crystallizes and forms solid；(3) sweating: after wax layer temperature reaches preset cooling final temperature, Bleed off pad water；Raw material is slowly heated to preset sweating final temperature again.In sweating effort, various components by fusing point by Low to high sequence be successively fused into liquid and flow out the wax layer residue (on wax) finally obtained (under wax) be exactly high-melting-point, The wax of low oil-containing；(4) it refines: collecting crude product and (continue to increase temperature after sweating effort, be taken out on wax with fusing, as Crude product), through clay-filtered (it be warming up to predetermined temperature after melting crude product, carclazyte is added and constant temperature was stirred to the predetermined time Filter afterwards) after, reshaping, packaging are purpose product.

Common sweating de-oiling technique can produce soap manufacturing paraffin and low melting point stone under solid-state with coarse flaky crystal structure Wax cannot but produce the microwax under solid-state with tiny needle-like crystal structure.Have experiments have shown that, common sweating de-oiling technique is raw When producing microwax, even if the oil content using the method for extending sweating sessions and improving sweating final temperature, on sweating later period wax Unrelated with yield, i.e., the oil content on wax does not decline with the decline of yield, so so far there are no with the production of sweating de-oiling technique The report of crystallite wax product.

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 production equipment；CN91206202(is a kind of High-efficient sweat pot for paraffin wax) improved on sweating process, but these methods there are still product yields lower, production cycle compared with The disadvantages of long, and cannot still produce microwax.

Sweating process is the unique solvent-free de-oiling method being currently known for commercial scale petroleum paraffin product, is being mentioned The today for advocating green low-carbon, environmental protection and energy saving, the demand using sweating de-oiling technique production microwax are more urgent.

Summary of the invention

In view of the deficiencies of the prior art, the present invention provides a kind of production method of microwax.Specifically use sweating Device is sent out after emulsion preferably is made with water or salting liquid in sweating raw material on the basis of common sweating de-oiling technique Sweat is conducive to the discharge of fluid oil；The oily to force point of liquid is carried out by wax layer using air-flow in sweating effort simultaneously From wax and oil, enhances separating effect and accelerate separating rate.The method of the present invention is low with equipment investment, production process is simple And operating cost is low, energy-saving safe and the advantages that solvent-free pollution.

The production method of microwax of the present invention, including the following contents:

A, first segment sweating, comprising:

Aa: emulsification

(Aa1) prepared by oil phase material: former as sweating less than the slack wax that 30%, melting range is 55 DEG C~80 DEG C using oil content Material, heating fusing；Oil soluble emulsifying agent is added, stirs evenly, forms oil phase material；

(Aa2) prepared by water-phase material: water or salting liquid being heated, water-phase material is formed；

(Aa3) prepared by emulsion: water-phase material being added in oil phase material under agitation, is continued after all adding Stirring 5~60 minutes；

Ab: sweating

(Ab1) emulsion of step (Aa3) preparation preparation: is packed into sweatbox；

(Ab2) emulsion first cooling-thermostatical crystallization: is cooled to by raw material slack wax with 5.0 DEG C/h~45.0 DEG C/h rate Within the scope of fusing point~+10 DEG C of fusing point, then raw material slack wax fusing point or less 8 DEG C~20 is cooled to 1.0 DEG C/h~4.0 DEG C/h rate DEG C predetermined temperature, and constant temperature is for a period of time；

(Ab3) heating-constant temperature sweating: with the heating of 0.5 DEG C/h~3.0 DEG C/h rate；Wax layer reaches predetermined temperature and perseverance Stop sweating after warm a period of time；Wax layer is forced air flow through in sweating effort；

(Ab4) it refines: collecting on wax, be intermediate products after refining；With

B, second segment sweating, comprising:

Ba: emulsification

(Ba1) prepared by oil phase material: the intermediate products obtained using first segment sweating is sweating raw materials, heating fusing；It is added Oil soluble emulsifying agent stirs evenly, and forms oil phase material；

(Ba2) prepared by water-phase material: water or salting liquid being heated, water-phase material is formed；

(Ba3) prepared by emulsion: water-phase material being added in oil phase material under agitation, is continued after all adding Stirring 5~60 minutes；

Bb: sweating

(Bb1) emulsion of step (Ba3) preparation preparation: is packed into sweatbox；

(Bb2) emulsion first cooling-thermostatical crystallization: is cooled to by intermediate products with 5.0 DEG C/h~45.0 DEG C/h rate Within the scope of fusing point~+10 DEG C of fusing point, then intermediate products fusing point or less 8 DEG C~20 is cooled to 1.0 DEG C/h~4.0 DEG C/h rate DEG C predetermined temperature, and constant temperature is for a period of time；

(Bb3) heating-constant temperature sweating: with the heating of 0.5 DEG C/h~3.0 DEG C/h rate；Wax layer reaches predetermined temperature and perseverance Stop sweating after warm a period of time；Wax layer is forced air flow through in sweating effort；

(Bb4) it refines: collecting on wax, be purpose product after refining.

In method of the invention, the sweating includes two sections of sweating efforts of process (A) and process (B).The first of process (A) Duan Fahan is for reducing raw material oil content and is enriched with purpose product, and the second segment sweating of process (B) continuation de-oiling production is micro- Brilliant wax product.The oil content (in mass) of process (A) the raw material slack wax less than 30%, melting range be generally 55 DEG C~ 80 DEG C can be decompression residuum through slack wax made from depitching matter, dewaxing.Process (B) raw material is obtained by first segment sweating Intermediate products.

In method of the invention, the HLB value of the oil soluble emulsifying agent is 1~10, preferably 3~8.Oil soluble surface Activating agent is selected from nonionic surface active agent, anionic surfactant, cationic surface active agent, amphoteric surface One or more of one group of substance that activating agent, response type surfactant active are constituted.The fusing point of the surfactant is solidifying Maximum temperature (i.e. step (Ab3) described in predetermined temperature) of the solid point lower than sweating heating in step (Ab3).The oil is molten Property emulsifier be preferably compound emulsifying agent that two or more surfactants are 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.

The response type surfactant active can be reacted with ammonia water by organic acid, and Organic Alcohol is added and is made.Specifically: Organic acid and ammonium hydroxide are stirred to react 5 under conditions of 10~30 DEG C~generate organic acid ammonium salt after sixty minutes；In 60~70 DEG C of item Under part, Organic Alcohol is added into the organic acid ammonium salt prepared, stirring is uniformly mixed it.The organic acid is Saturation and unsaturated acids of the carbon number 1~36, preferably unitary organic acid of the carbon number 8~20, can be caprylic acid, the positive tenth of the twelve Earthly Branches acid, N-capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitinic acid, stearic acid, linoleic acid, oleic acid, nonadecanoic acid, Or mixtures thereof one of arachidic acid；Be also possible to one of the oxalic acid of polyacid, malic acid, maleic acid, fumaric acid or Its mixture.The mass concentration of the ammonium hydroxide is 1%~28%, preferably 5%~15%.The Organic Alcohol is carbon number 1~12 Or mixtures thereof one of saturated monohydroxy alcohol, preferably methanol, ethyl alcohol.The mixing speed is 50~1500r/min, preferably 100~1000r/min.It uses in the sweating effort of reactive emulsifier with the mass ratio of the acid such as sulfuric acid, nitric acid as 2%~20% Aqueous solution absorb ammonia.

In the present invention, in the preparation process of the oil phase material, the preparation temperature of emulsion is generally 70 DEG C~95 DEG C.

In method of the invention, the salting liquid be any water-soluble salt solution, preferably chemical property it is stable, it is nontoxic, It is non-corrosive, without special odor, salting liquid cheap and easy to get, can be sodium chloride, potassium chloride, sodium carbonate, potassium carbonate, sulfuric acid The aqueous solution of or mixtures thereof one of sodium, potassium sulfate, salting liquid mass concentration are 1%~20%, preferably 5%~15%.It is described Emulsion ratio are as follows: sweating material quality percentage 60.0%~90.0%, preferably 65.0%~84.0%, water or salting liquid quality Percentage is 9.9%~30.0%, preferably 15.0%~30.0%, and compound emulsifying agent mass percent is 0.1%~10.0%, preferably 1.0%~5.0%；The emulsification condition be at 70 DEG C~95 DEG C, with 50~1500 revs/min of mixing speed mixing 5~ It 60 minutes, preferably at 75 DEG C~90 DEG C, is mixed 10~30 minutes with 100~1000 revs/min of mixing speed.

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.In step (Ab3) and step (Bb3) sweating effort, described forces air flow through wax layer Using increasing air pressure above wax layer and/or reducing air pressure below wax layer, so that wax layer upper and lower is formed pressure difference and realize.Institute The pressure difference stated is generally 0.1~5.0 atmospheric pressure, preferably 0.2~2.0 atmospheric pressure, to force air flow through wax layer.

In method of the invention, in step (Ab2) and step (Bb2) the raw material wax layer crystallization process, preferred raw material wax Layer is first to cool down thereafter within the scope of 10.0 DEG C/h~40.0 DEG C/h rate fast cooling to sweating raw material fusing point~+5 DEG C of fusing point Rate preferably 1.5 DEG C/h~3.5 DEG C/h.The predetermined temperature of cooling described in step (Ab2) be preferably shorter than 10 DEG C of slack wax fusing point~ 15℃；And the predetermined temperature of step (Bb2) described cooling is preferably shorter than 10 DEG C~15 DEG C of intermediate products fusing point.

In method of the invention, after being cooled to predetermined temperature in step (Ab2) and step (Bb2), preferably increase constant temperature Stage is so that solid crystal is more abundant.The time in constant temperature stage is 0.1~3.0 hour, preferably 1.0~3.0 hours.

In method of the invention, the heating rate preferably 1.0 DEG C/h of raw material wax layer in step (Ab3) and step (Bb3) ~2.5 DEG C/h.The predetermined temperature to heat up in step (Ab3) is lower than 2 DEG C~10 DEG C of fusing point of intermediate products, in step (Bb3) The predetermined temperature of heating is lower than 2 DEG C~10 DEG C of fusing point of purpose product.

In method of the invention, after being warming up to preset temperature in step (Ab3) and step (Bb3), preferably increase constant temperature Stage, time in constant temperature stage was 0.1~5.0 hour so that the separation of wax and oil is more abundant, preferably 0.5~5.0 hour, most Preferably 1.0~5.0 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, collet, disk Pipe etc. can make wax layer lifting/lowering temperature process faster, wax layer more uniform temperature；The circulatory system has program cooling/heating function, circulation The substances such as water or conduction oil are added as circulatory mediator in system.

In method of the invention, forcing air flow through wax layer described in step (Ab3) and step (Bb3) can be in sweating Process any stage is implemented, and preferably implements at sweating initial stage.

In method of the invention, wax layer is forced air flow through described in step (Ab3) and step (Bb3) and is utilized in wax Layer top increases what air pressure was realized, can such as apply the pressure of 0.2~2.0 atmospheric pressure (gauge pressure) above wax layer, and under wax layer Side remains normal pressure.

In method of the invention, wax layer is forced air flow through described in step (Ab3) and step (Bb3) and is utilized in wax Layer lower section reduces what air pressure was realized, and normal pressure can be such as kept above wax layer, and -0.2~-1.0 atmosphere are maintained below wax layer Press the pressure of (gauge pressure).

Sweating de-oiling method be separated using wax and oil property with different melting points to produce pertroleum wax, but for Slack wax made from decompression residuum, since its main component is isoparaffin and cycloalkane, chemical composition is complicated, brilliant when causing to crystallize Body structure is more fine and compact, forms huge filter flow resistance power to the discharge of fluid oil, this is resulted in only by gravity natural separation Common sweating effort in wax and oil be difficult to be kept completely separate.Therefore common sweating de-oiling technique, which cannot produce, meets relevant criterion Crystallite wax product.

The present invention is in order to allow this solvent-free de-oiling method of sweating to produce crystallite wax product, by common sweating The further investigation of journey is difficult to the reason of separating for wax and oil, by using air-flow to pass through wax layer in sweating effort；Increase knot The constant temperature stage of brilliant process is conducive to keep wax layer crystallization more abundant, and the constant temperature stage for increasing sweating effort is conducive to wax and oily and fills Separation.Raw material and water or salting liquid are further preferably formed into w/o type emulsification under the compound emulsifying agent effect of appropriate HLB value simultaneously Liquid is uniformly distributed water or salting liquid in the feed in the form of fine particle；Using air-flow by wax layer in sweating effort, one Aspect can carry water outlet or salting liquid to form short space in wax layer, these short spaces are easy in sweating effort in wax Several tiny channels are formed in layer, are conducive to discharge oily in sweating effort；Another aspect air-flow can carry out the oil of liquid To force separation wax and oil, to enhance separating effect and accelerate separating rate.It selects salting liquid as water phase, increases The difference in specific gravity of water phase and oily phase, can accelerate the velocity of discharge of the water phase in sweating effort, to form the channel of oil extraction as early as possible.It is selected Surfactant fusing point or freezing point are lower than the maximum temperature of step (Ab3) sweating effort, and contain functional group, with sweating raw material Intermiscibility it is poor, can be discharged in sweating effort with fluid oil.It is micro- that these improvement produce sweating de-oiling technique Brilliant 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；Water or the salting liquid shape in wax layer are utilized simultaneously At evenly dispersed short space, it is also beneficial to the quick discharge of oil, so that sweating de-oiling technique be allow to produce microwax production Product.Method of the invention has that plant investment is low, production process is simple and operating cost is low, safety, energy conservation and solvent-free pollution The advantages that environment.

Specific embodiment

Sweating ware top connects dismountable sealing device and connect with pressurized buffer tank and compressor, and/or in sweating Ware lower part connects pressure-reducing cushioning tank and vacuum pump；Sweating ware is packed into after sweating raw material and the emulsification of water or salting liquid；It is controlled with water-bath Wax layer heating-cooling speed；Wax layer temperature is down to preset temperature and constant temperature for a period of time；In sweating effort, start compressor with 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 and constant temperature stops sweating effort afterwards for a period of time；By two sections of sweating degreasing process, on wax It is crystallite wax product after refining.

1-2 illustrates the production method of microwax of the present invention by the following examples.

Comparative example 1

This comparative example includes A: first segment sweating and B: second segment sweating two parts.

A: first segment sweating

This process includes: (A1) preparation, (A2) cooling-thermostatical crystallization, (A3) heating-constant temperature sweating, (A4) essence The processes such as system.

(A1) preparation

Water is padded below sweating ware ware plate.The sealing system of sweating ware and pressurized buffer tank and compressor are connected；It is sending out Sweat ware lower part installation pressure-reducing cushioning tank simultaneously connects vacuum pump；Sweating ware collet and removable coil pipe are connect with the circulatory system, it will Coil pipe is fixed on sweating ware；Using water as heat medium, start the heating function of the circulatory system, recirculated water is made to be warming up to 66 DEG C.

Take Daqing crude oil decompression residuum slack wax (initial boiling point: 420 DEG C, 90% distillate a little: 550 DEG C；63.0 DEG C of fusing point；Oil content 20.3%) 80.0Kg is raw material, and sweating ware is added after being heated to 66 DEG C of fusings.

(A2) cooling-thermostatical crystallization

Start the circulatory system refrigerating function, control wax layer temperature with the rate of temperature fall of 2.0 DEG C/h drop to 52.0 DEG C with Make wax layer crystallize to form solid, and constant temperature 1.0 hours so that wax layer sufficient crystallising.Close the refrigerating function of the circulatory system.

(A3) heating-constant temperature sweating

Sweating ware is discharged and pads water.Sweating ware outlet connection intermediate storage tank (I) is to receive under wax；The close of sweating ware top is installed Envelope system；Starting compressor simultaneously keeps pressurized buffer pressure inside the tank to stablize in 1.3~1.5 atmospheric pressure (gauge pressure), sweating ware ware Normal pressure is kept below plate.Start circulation system function, so that wax layer temperature is increased to 62.0 with the heating rate of 2.0 DEG C/h ℃.Stop compressor.

Starting vacuum pump simultaneously keeps pressure-reducing cushioning pressure inside the tank to stablize on -0.5~-0.7 atmospheric pressure (gauge pressure), wax layer Square air pressure keeps normal pressure；Continue to make with the heating rate of 2.0 DEG C/h wax layer temperature to be increased to 72.0 DEG C and constant temperature 2.0 hours so that Wax in wax layer is sufficiently separated with oil.Stop vacuum pump, terminates sweating effort.

The outlet of sweating ware is changed to connect thick intermediate products storage tank (I) to receive on wax.Continue to increase circulating water temperature to 90 DEG C, it is taken out on wax with fusing, as thick intermediate products (I).

(A4) it refines

Thick intermediate products (I) through it is clay-filtered be intermediate products (I), it is stand-by after molding.

Intermediate products (I) property: fusing point: 76.5 DEG C, oil content: 7.52%.Intermediate products (I) yield is 15.1%(phase For raw material slack wax).

B: second segment sweating

This process includes: (B1) preparation, (B2) cooling-thermostatical crystallization, (B3) heating-constant temperature sweating, (B4) essence The processes such as system.

(B1) preparation

Water is padded below sweating ware ware plate.The sealing system of sweating ware and pressurized buffer tank and compressor are connected；It is sending out Sweat ware lower part installation pressure-reducing cushioning tank simultaneously connects vacuum pump；Sweating ware collet and removable coil pipe are connect with the circulatory system, it will Coil pipe is fixed on sweating ware；Using water as heat medium, start the heating function of the circulatory system, recirculated water is made to be warming up to 80 DEG C.

With the product (intermediate products (I)) of first segment sweating for raw material, sweating ware is added after being heated to 80 DEG C of fusings.

(B2) cooling-thermostatical crystallization

Start the circulatory system refrigerating function, with the rate of temperature fall of 2.0 DEG C/h make wax layer temperature drop to 66.0 DEG C so that Wax layer crystallizes to form solid, and constant temperature 1.0 hours so that wax layer sufficient crystallising.Close the refrigerating function of the circulatory system.

(B3) heating-constant temperature sweating

Sweating ware is discharged and pads water.Sweating ware outlet connection intermediate storage tank (II) is to receive under wax；Sweating ware top is installed Sealing system；Starting compressor simultaneously keeps pressurized buffer pressure inside the tank to stablize in 1.3~1.5 atmospheric pressure (gauge pressure), sweating ware Normal pressure is kept below ware plate.Start circulation system function, so that wax layer temperature is increased to 70.0 with the heating rate of 1.5 DEG C/h ℃.Stop compressor.

Starting vacuum pump simultaneously keeps pressure-reducing cushioning pressure inside the tank to stablize on -0.5~-0.7 atmospheric pressure (gauge pressure), wax layer Square air pressure keeps normal pressure；Continue to make with the heating rate of 1.5 DEG C/h wax layer temperature to be increased to 74.0 DEG C and constant temperature 4.0 hours so that Wax in wax layer is sufficiently separated with oil.Stop vacuum pump, terminates sweating effort.

The outlet of sweating ware is changed to connection crude product storage tank (I) to receive on wax.Continue increase circulating water temperature to 90 DEG C, with Fusing is taken out on wax, as crude product (I).

(B4) it refines

Crude product (I) is crystallite wax product (I) after clay-filtered, molding and packaging.

Crystallite wax product (I) property: fusing point: 77.3 DEG C, oil content: 1.40%, needle penetration 18(1/10mm).Meet commodity 80^#The associated specifications of microwax primes.The yield of crystallite wax product (I) is 7.2%(relative to raw material slack wax).

Embodiment 1

The present embodiment includes: A: first segment sweating and B: second segment sweating two parts.

A, first segment sweating, including Aa: emulsification and Ab: sweating two parts:

Aa: emulsification

This part includes three preparation of (Aa1) oil phase material, the preparation of (Aa2) water-phase material, (Aa3) emulsion preparation steps Suddenly.

(Aa1) prepared by oil phase material: taking Daqing crude oil decompression residuum slack wax (with comparative example 1) 80.0Kg, is heated to 80 DEG C Sorbitan monooleate 2.5Kg, fatty alcohol sulfate monoethanolamine 0.5Kg are added after fusing, stirs evenly.

(Aa2) prepared by water-phase material: the water of 17.0Kg is heated to 90 DEG C.

(Aa3) prepared by emulsion: with the oil phase material of speed stirring (Aa1) preparation of 500r/min, and will make in (Aa2) Standby water-phase material is slowly added into the oil phase material prepared in (Aa1), is continued to stir 30min, is formed water-in-oil emulsion Liquid.

Ab: sweating

This part includes (Ab1) preparation, (Ab2) cooling-thermostatical crystallization, (Ab3) heating-constant temperature sweating, (Ab4) essence Make four steps.

(Ab1) preparation

Water is padded below sweating ware ware plate.The sealing system of sweating ware and pressurized buffer tank and compressor are connected；It is sending out Sweat ware lower part installation pressure-reducing cushioning tank simultaneously connects vacuum pump；Sweating ware collet and removable coil pipe are connect with the circulatory system, it will Coil pipe is fixed on sweating ware.Using water as heat medium.The heating function for starting the circulatory system, makes recirculated water be warming up to 66 DEG C. Sweating ware is added in the emulsion prepared in (Aa3).

(Ab2) cooling-thermostatical crystallization

Emulsion stands the refrigerating function of the starting circulatory system after 1h, controls wax layer temperature with the rate of temperature fall of 2.0 DEG C/h Drop to 52.0 DEG C so that wax layer crystallizes to form solid, and constant temperature 1.0 hours so that wax layer sufficient crystallising.Close the circulatory system Refrigerating function.

(Ab3) heating-constant temperature sweating

Sweating ware is discharged and pads water.Sweating ware outlet connection intermediate storage tank (III) is to receive under wax；Sweating ware top is installed Sealing system；Starting compressor simultaneously keeps pressurized buffer pressure inside the tank to stablize in 1.3~1.5 atmospheric pressure (gauge pressure), sweating ware Normal pressure is kept below ware plate.Start circulation system function, so that wax layer temperature is increased to 62.0 with the heating rate of 2.0 DEG C/h ℃.Stop compressor.

Starting vacuum pump simultaneously keeps pressure-reducing cushioning pressure inside the tank to stablize on -0.5~-0.7 atmospheric pressure (gauge pressure), wax layer Square air pressure keeps normal pressure；Continue to make with the heating rate of 2.0 DEG C/h wax layer temperature to be increased to 72.0 DEG C and constant temperature 2.0 hours so that Wax in wax layer is sufficiently separated with oil.Stop vacuum pump, terminates sweating effort.

The outlet of sweating ware is changed to connect thick intermediate products storage tank (II) to receive on wax.Continue to increase circulating water temperature to 90 DEG C, it is taken out on wax with fusing, as thick intermediate products (II).

(Ab4) it refines

Thick intermediate products (II) through it is clay-filtered be intermediate products (II), it is stand-by after molding.

Intermediate products (II) property: fusing point: 76.3 DEG C, oil content: 5.00%.Intermediate products (II) yield is 18.7% (relative to raw material slack wax).

B, second segment sweating, including Ba: emulsification and Bb: sweating two parts.

Ba: emulsification

This part includes three preparation of (Ba1) oil phase material, the preparation of (Ba2) water-phase material, (Ba3) emulsion preparation steps Suddenly.

(Ba1) prepared by oil phase material: with product (intermediate products (II)) 80.0Kg of first segment sweating, being heated to 80 DEG C and melts Tetraethylene glycol monostearate 2.0Kg, triacetamide oleate 1.5Kg are added after change, stirs evenly.

(Ba2) prepared by water-phase material: the KCl of 1.5Kg being dissolved in the water of 15Kg, and is heated to 90 DEG C.

(Ba3) prepared by emulsion: with the oil phase material of speed stirring (Ba1) preparation of 800r/min, and will make in (Ba2) Standby water-phase material is slowly added into the oil phase material prepared in (Ba1), is continued to stir 30min, is formed water-in-oil emulsion Liquid.

Bb: sweating

This part includes (Bb1) preparation, (Bb2) cooling-thermostatical crystallization, (Bb3) heating-constant temperature sweating, (Bb4) essence Make four steps.

(Bb1) preparation

Water is padded below sweating ware ware plate.The sealing system of sweating ware and pressurized buffer tank and compressor are connected；It is sending out Sweat ware lower part installation pressure-reducing cushioning tank simultaneously connects vacuum pump；Sweating ware collet and removable coil pipe are connect with the circulatory system, it will Coil pipe is fixed on sweating ware.Using water as heat medium.The heating function for starting the circulatory system, makes recirculated water be warming up to 80 DEG C. Sweating ware is added in the emulsion prepared in (Ba3).

(Bb2) cooling-thermostatical crystallization

Emulsion stands the refrigerating function for starting the circulatory system after 1h, at a temperature of making wax layer with the rate of temperature fall of 2.0 DEG C/h 66.0 DEG C are down to so that wax layer crystallizes to form solid, and constant temperature 1.0 hours so that wax layer sufficient crystallising.Close the system of the circulatory system Cold function.

(Bb3) heating-constant temperature sweating

Sweating ware is discharged and pads water.Sweating ware outlet connection intermediate storage tank (IV) is to receive under wax；Sweating ware top is installed Sealing system；Starting compressor simultaneously keeps pressurized buffer pressure inside the tank to stablize in 1.3~1.5 atmospheric pressure (gauge pressure), sweating ware Normal pressure is kept below ware plate.Start circulation system function, so that wax layer temperature is increased to 70.0 with the heating rate of 1.5 DEG C/h ℃.Stop compressor.

Starting vacuum pump simultaneously keeps pressure-reducing cushioning pressure inside the tank to stablize on -0.5~-0.7 atmospheric pressure (gauge pressure), wax layer Square air pressure keeps normal pressure；Continue to make with the heating rate of 1.5 DEG C/h wax layer temperature to be increased to 74.0 DEG C and constant temperature 4.0 hours so that Wax in wax layer is sufficiently separated with oil.Stop vacuum pump, terminates sweating effort.

The outlet of sweating ware is changed to connection crude product storage tank (II) to receive on wax.Continue increase circulating water temperature to 90 DEG C, It is taken out on wax with fusing, as crude product (II).

(Bb4) it refines

Crude product (II) is crystallite wax product (II) after clay-filtered.

Crystallite wax product (II) property: fusing point: 77.4 DEG C, oil content: 1.20%.Needle penetration 17(1/10mm).Meet quotient The associated specifications of product 80# microwax primes.The yield of crystallite wax product (II) is 12.3%(relative to raw material slack wax).

Embodiment 2

The present embodiment includes: A: first segment sweating and B: second segment sweating two parts.

A, first segment sweating, including Aa: emulsification and Ab: sweating two parts:

Aa: emulsification

This part includes three preparation of (Aa1) oil phase material, the preparation of (Aa2) water-phase material, (Aa3) emulsion preparation steps Suddenly.

(Aa1) prepared by oil phase material: taking Daqing crude oil decompression residuum slack wax (with comparative example 1) 80.0Kg, is heated to 80 DEG C Sorbitan monostearate 2.5Kg, dodecyldimethyl ammonium oxide 0.5Kg are added after fusing, stirs evenly.

(Aa2) prepared by water-phase material: the water of 17Kg is heated to 95 DEG C.

(Aa3) prepared by emulsion: with the oil phase material of speed stirring (Aa1) preparation of 1000r/min, and will be in (Aa2) The water-phase material of preparation is slowly added into the oil phase material prepared in (Aa1), continues to stir 50min, forms water-in-oil type cream Change liquid.

Ab: sweating

With embodiment 1.

Intermediate products (III) property manufactured in the present embodiment: fusing point: 76.4 DEG C, oil content: 5.06%.Intermediate products (III) Yield is 19.3%(relative to raw material slack wax).

B, second segment sweating, including B0: the preparation of emulsifier, Ba: emulsification and Bb: sweating three parts.

B0: the preparation of emulsifier: the oleic acid of the linoleic acid and 2Kg that weigh 3Kg is placed in reaction kettle, is added after being warming up to 30 DEG C Enter 10% ammonium hydroxide 2.5Kg, starting is stirred, mixing speed 500r/min, and temperature is risen to 60 DEG C after reaction 60min, is added It is stand-by after mixing to continue stirring 30min for the ethyl alcohol of 0.75Kg.

Ba: emulsification

This part includes three preparation of (Ba1) oil phase material, the preparation of (Ba2) water-phase material, (Ba3) emulsion preparation steps Suddenly.

(Ba1) prepared by oil phase material: with product (intermediate products (III)) 80.0Kg of first segment sweating, being heated to 90 DEG C and melts The emulsifier 3.0Kg of B0 process preparation is added after change, stirs evenly.

(Ba2) prepared by water-phase material: by the K of 2Kg₂SO₄It is dissolved in the water of 15Kg, and is heated to 90 DEG C.

(Ba3) prepared by emulsion: with the oil phase material of speed stirring (Ba1) preparation of 500r/min, and will make in (Ba2) Standby water-phase material is slowly added into the oil phase material prepared in (Ba1), is continued to stir 30min, is formed water-in-oil emulsion Liquid.

Bb: sweating

With 5%H in sweating effort₂SO₄Solution absorbs ammonia, remaining is the same as embodiment 1.

Crystallite wax product (III) property manufactured in the present embodiment: fusing point: 77.2 DEG C, oil content: 1.22%.Needle penetration 17 (1/10mm).Meet the associated specifications of commodity 80# microwax primes.The yield of crystallite wax product (III) is 12.1% (relative to raw material slack wax).

The production method that can be seen that microwax of the present invention by embodiment and comparative example, by increase pressurization and/or very The improvement to sweatbox such as empty facility；Using the water or salting liquid of emulsification formed in wax layer evenly dispersed short space, The improvement to sweating process such as wax layer, the constant temperature stage for increasing crystallization and sweating effort is forced air flow through in sweating effort； It enhances the separating effect of wax and oil and accelerates separating rate, so that sweating de-oiling technique be allow to produce crystallite wax product.

Claims (23)

1. a kind of production method of microwax, including the following contents:

A, first segment sweating, comprising:

Aa: emulsification

(Aa1) oil phase material prepare: using oil content less than 30%, melting range be 55 DEG C~80 DEG C slack wax as sweating raw material, add Heat fusing；Oil soluble emulsifying agent is added, stirs evenly, forms oil phase material；

(Aa2) prepared by water-phase material: water or salting liquid being heated, water-phase material is formed；

(Aa3) prepared by emulsion: water-phase material being added in oil phase material under agitation, continues to stir after all adding 5~60 minutes；

Ab: sweating

(Ab1) emulsion of step (Aa3) preparation preparation: is packed into sweatbox；

(Ab2) emulsion first cooling-thermostatical crystallization: is cooled to by raw material slack wax fusing point with 5.0 DEG C/h~45.0 DEG C/h rate Within the scope of+10 DEG C of~fusing point, then with 1.0 DEG C/h~4.0 DEG C/h rate it is cooled to 8 DEG C~20 DEG C of raw material slack wax fusing point or less Predetermined temperature, and constant temperature 0.1~3.0 hour；

(Ab3) heating-constant temperature sweating: with the heating of 0.5 DEG C/h~3.0 DEG C/h rate；Wax layer reaches predetermined temperature and constant temperature 0.1 Stop sweating after~5.0 hours；Wax layer is forced air flow through in sweating effort；The predetermined temperature is lower than intermediate products 2 DEG C~10 DEG C of fusing point；

(Ab4) it refines: collecting on wax, be intermediate products after refining；With

B, second segment sweating, comprising:

Ba: emulsification

(Ba1) prepared by oil phase material: the intermediate products obtained using first segment sweating is sweating raw materials, heating fusing；It is molten that oil is added Property emulsifier, stir evenly, formed oil phase material；

(Ba2) prepared by water-phase material: water or salting liquid being heated, water-phase material is formed；

(Ba3) prepared by emulsion: water-phase material being added in oil phase material under agitation, continues to stir after all adding 5~60 minutes；

Bb: sweating

(Bb1) emulsion of step (Ba3) preparation preparation: is packed into sweatbox；

(Bb2) cooling-thermostatical crystallization: with 5.0 DEG C/h~45.0 DEG C/h rate by emulsion be cooled to intermediate products fusing point~ Within the scope of+10 DEG C of fusing point, then 8 DEG C~20 DEG C of intermediate products fusing point or less pre- be cooled to 1.0 DEG C/h~4.0 DEG C/h rate Determine temperature, and constant temperature 0.1~3.0 hour；

(Bb3) heating-constant temperature sweating: with the heating of 0.5 DEG C/h~3.0 DEG C/h rate；Wax layer reaches predetermined temperature and constant temperature one Stop sweating after the section time；Wax layer is forced air flow through in sweating effort；The predetermined temperature is molten lower than purpose product 2 DEG C~10 DEG C of point；

(Bb4) it refines: collecting on wax, be purpose product after refining；

Wherein, the salting liquid in sodium chloride, potassium chloride, sodium carbonate, potassium carbonate, sodium sulphate and potassium sulfate at least one The aqueous solution of kind.

2. according to the method for claim 1, which is characterized in that the oil soluble emulsifying agent is living selected from non-ionic surface Property agent, anionic surfactant, cationic surface active agent, amphoteric surfactant, response type surfactant active The one group of substance constituted；The HLB value of oil soluble emulsifying agent is 1~10, and the fusing point or freezing point of the oil soluble emulsifying agent are lower than The maximum temperature of step (Ab3) sweating heating.

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, alkyl imidazoline derivatives, derivative of fatty acid, both sexes One group of substance that type modified epoxy ethane additive product 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 the mass concentration of the salting liquid is 1%~20%.

6. according to the method for claim 1, which is characterized in that mixing speed described in step (Aa3) and step (Ba3) It is 50~1500 revs/min, the preparation temperature of emulsion is 70 DEG C~95 DEG C.

7. according to the method for claim 1, which is characterized in that step (Aa3) and step (Ba3) obtain the composition of emulsion Are as follows: sweating material quality percentage is 60.0%~90.0%, and the mass percent of water or salting liquid is 9.9%~30.0%, emulsification The mass percent of agent is 0.1%~10.0%.

8. according to the method for claim 7, which is characterized in that the composition of the emulsion are as follows: sweating material quality percentage Number is 65.0%~84.0%, and the mass percent of water or salting liquid is 15.0%~30.0%, and the mass percent of emulsifier is 1.0%~5.0%.

9. according to the method for claim 1, which is characterized in that pressure air-flow described in step (Ab3) and step (Bb3) It is used by wax layer and increases air pressure above wax layer and/or reduce air pressure below wax layer, wax layer upper and lower is made to form pressure difference It realizes, the pressure difference is 0.1~5.0 atmospheric pressure.

10. according to the method for claim 1, which is characterized in that the predetermined temperature of cooling described in step (Ab2) is lower than original 10 DEG C~15 DEG C of slack wax fusing point of material；And the predetermined temperature of cooling described in step (Bb2) is lower than intermediate products fusing point 10 DEG C~15 ℃。

11. according to the method for claim 1, which is characterized in that force air-flow described in step (Ab3) and step (Bb3) Implemented by wax layer at sweating initial stage.

12. according to the method for claim 9, which is characterized in that pressure gas described in step (Ab3) and step (Bb3) Stream is used by wax layer increases air pressure realization above wax layer, applies the gauge pressure pressure of 0.2~2.0 atmospheric pressure above wax layer Power, and normal pressure is remained below wax layer.

13. according to the method for claim 9, which is characterized in that pressure gas described in step (Ab3) and step (Bb3) Stream is used by wax layer reduces air pressure realization below wax layer, and air pressure keeps normal pressure above wax layer, and maintained below wax layer- The gauge of 0.2~-1.0 atmospheric pressure.

14. according to the method for claim 2, which is characterized in that the response type surfactant active is by organic acid and ammonia Water reaction, and Organic Alcohol is added and is made: organic acid and ammonium hydroxide is stirred to react 5 under conditions of 10~30 DEG C~it generates after sixty minutes Organic acid ammonium salt；Under conditions of 60~70 DEG C, Organic Alcohol is added into the organic acid ammonium salt prepared, stirring makes it in 5~30 minutes It is uniformly mixed to get response type surfactant active is arrived.

15. according to the method for claim 14, which is characterized in that the organic acid be carbon number 1~36 saturation and Unsaturated acids.

16. according to the method for claim 15, which is characterized in that the organic acid is selected from caprylic acid, acid of the positive tenth of the twelve Earthly Branches, the positive last of the ten Heavenly stems Acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitinic acid, stearic acid, linoleic acid, oleic acid, nonadecanoic acid, peanut Acid, oxalic acid, malic acid, maleic acid, fumaric acid constitute one or more of one group of substance.

17. according to the method for claim 14, which is characterized in that the mass concentration of the ammonium hydroxide is 1%~25%.

18. according to the method for claim 14, which is characterized in that the Organic Alcohol is saturation one of the carbon number 1~12 First alcohol.

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 5, which is characterized in that the mass concentration of the salting liquid is 5%~15%.

21. according to the method for claim 9, which is characterized in that the pressure difference is 0.2~2.0 atmospheric pressure.

22. according to the method for claim 15, which is characterized in that the organic acid be carbon number 8~20 unitary or Multicomponent organic acid.

23. according to the method for claim 18, which is characterized in that the Organic Alcohol is methanol and/or ethyl alcohol.