阅读说明：本技术 烛光用蜡及其制备方法 (Candle wax and preparation method thereof ) 是由 李俊诚 苗恒 钱震 周岩 菅青娥 马国清 郑会月 郭良兰 王海国 于 2019-09-24 设计创作，主要内容包括：一种烛光用蜡及其制备方法,所述制备方法包括：(1)将费托合成产物经催化加氢得到费托精制蜡；(2)将所述费托精制蜡经蒸馏分离出馏程在300-520℃内的多个窄馏分；(3)利用一个窄馏分或多个窄馏分的混合物制备烛光用蜡。本发明工艺简单,操作灵活性强,产品种类丰富。(A candle wax and a method for making the same, the method comprising: (1) carrying out catalytic hydrogenation on the Fischer-Tropsch synthesis product to obtain Fischer-Tropsch refined wax; (2) separating a plurality of narrow fractions with the distillation range of 300-520 ℃ from the Fischer-Tropsch refined wax by distillation; (3) candle wax is prepared using a narrow cut or a mixture of narrow cuts. The invention has simple process, strong operation flexibility and rich product types.)

1. A method of making candle wax, comprising:

(1) carrying out catalytic hydrogenation on the Fischer-Tropsch synthesis product to obtain Fischer-Tropsch refined wax;

(2) separating a plurality of narrow fractions with the distillation range of 300-520 ℃ from the Fischer-Tropsch refined wax by distillation;

(3) candle wax is prepared using a narrow cut or a mixture of narrow cuts.

2. The preparation method according to claim 1, wherein the distillation manner in the step (2) is selected from atmospheric/vacuum distillation, short path molecular distillation, thin film distillation or any combination thereof, preferably, the distillation in the step (2) is operated at a pressure of 0.1PaA (absolute pressure) to atmospheric pressure.

3. The method of claim 1, wherein the narrow fraction has a distillation range width of 10-100 ℃, such as 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃.

4. The production method according to claim 1, wherein in the step (3), the narrow fraction or the mixture of narrow fractions having a melting point of 30 to 50 ℃ is directly used as the low melting candle wax.

5. The method of claim 1, wherein the high melting candle wax is obtained by deoiling a narrow fraction or a mixture of narrow fractions having a melting point of 50-65 ℃ in step (3).

6. The production process according to claim 5, wherein in the step (3), the mode of deoiling is fractional crystallization.

7. The production method according to claim 6, wherein the step of fractional crystallization comprises: crystallizing the narrow fraction at a temperature of 5-10 deg.C below the melting point of the narrow fraction, maintaining the temperature for 1-10h (such as 2h, 3h, 4h, 6h, 8h), and discharging mother liquor residue; then the temperature of the crystal is raised to sweat, and finally the temperature is raised to the melting point; finally heating up the crystal to melt and discharge the material to obtain candle wax; wherein, preferably, the temperature rise comprises a plurality of temperature gradients.

8. A candle wax prepared by the preparation method according to claims 1 to 7, wherein the candle wax is a low melting point candle wax or a high melting point candle wax.

9. The candle wax according to claim 8, wherein the low melting candle wax comprises tea wax or cupped wax.

10. The candle wax according to claim 8, wherein the high melting point candle wax comprises a dewaxed cup wax or an LED process wax; preferably, the oil content of the high melting candle wax is below 2 wt%, and the penetration @25 ℃ is less than or equal to 25, and the unit is 1/10 mm.

Technical Field

The invention belongs to the technical field of chemical industry, and particularly relates to candle wax and a preparation method thereof.

Background

Paraffin wax as a traditional wax material plays an important role in the candle manufacturing history, but with the improvement of environmental protection consciousness and health consciousness of consumers, a series of problems are gradually exposed to paraffin wax type candles. Firstly, the paraffin is used as a byproduct in the petroleum refining process and has non-regenerability; secondly, black smoke is generated in the combustion process of the paraffin wax candle, wherein the black smoke contains harmful substances such as polycyclic aromatic hydrocarbon, metal ions, sulfur-containing compounds and the like, and the substances seriously damage the health of human bodies; moreover, if these harmful substances are removed from the paraffin, the production process is complicated. The Fischer-Tropsch synthesis product is a methylene polymer, alkane mixtures obtained by catalytic polymerization reaction of synthesis gas at medium temperature and medium pressure are primarily separated to obtain Fischer-Tropsch synthesis stable light hydrocarbons, liquid paraffin, soft wax, Fischer-Tropsch synthesis wax and the like, and the products have low content of impurities such as aromatic hydrocarbon, sulfur, nitrogen and the like, so the Fischer-Tropsch synthesis product is an ideal environment-friendly candle raw material.

The paraffin wax used for candle production has various practical purposes and different quality requirements, and the quality of the common candle mainly depends on the components of the paraffin wax raw material and the high and low melting point. The candle is produced by using paraffin as raw material, refining the paraffin, cutting into several types with melting points of 52, 54, 56, 58 and 60, etc., or mixing the paraffin with different melting points according to different proportions. The filling candle (not taking out of cup candle) requires that the melting point of the raw material wax is lower than 55 ℃, has certain requirements on the flash point, and ensures the safety of combustion (prevents flash explosion).

Patent CN101870888B provides a candle wax blend containing, on a mass basis, from 2% to 40% of a medium heavy wax fraction obtained by a distillation operation, the medium heavy wax fraction having a congealing point in the range of 76 to 84 ℃ and a normal paraffin content of at least 80% (wt%). The wax blend also contains 60% to 98% of a medium wax fraction obtained as a result of the same distillation operation as that used to obtain the medium heavy wax fraction, a congealing point in the range of 55-65 ℃ and an n-paraffin content of at least 80% (wt%).

The patent CN101724511A provides a candle raw material composition and a preparation method thereof, which is characterized in that Fischer-Tropsch synthesis refined wax and Fischer-Tropsch synthesis cracked wax are mixed according to a certain proportion to obtain a candle raw material, the Fischer-Tropsch synthesis refined wax is obtained by hydrofining Fischer-Tropsch synthesis crude wax, and the Fischer-Tropsch synthesis cracked wax is obtained by hydrocracking Fischer-Tropsch synthesis refined wax whole fraction or heavy fraction.

The candle light special wax can be widely used in various craft candles, and the product performance can be regulated and controlled by the raw material component proportion according to the downstream product application. The prior art for producing candle special wax mainly has the following defects:

(1) the traditional candle preparation method is prepared by petroleum fractionation components, and due to the complexity of the petroleum composition, the problems of complex process and environmental pollution caused by the burning process are usually existed in the candle preparation process.

(2) The candle is prepared by adopting the Fischer-Tropsch synthesis refined wax and the Fischer-Tropsch synthesis cracked wax composition, wherein the cracked wax needs to be subjected to high-pressure hydrocracking operation, the production process has harsh operating conditions and potential safety hazards.

(3) In the candle wax blend, the medium and heavy wax fractions are mixed to prepare the candle wax with high melting point, which is mainly applicable to the field of candle wax with low requirements on oil production.

Other deoiling operations for candle waxes, including solvent deoiling and sweating deoiling, have become unattractive from environmental and production cycle points.

Technical terms:

Fischer-Tropsch synthesis product: synthesis gas (CO and H)₂) Under the action of catalyst and certain temp. and pressure, the paraffin mixture obtained by F-T reaction is passed through the process of hydrorefining to remove olefin and oxygen-containing compound, so that the high-carbon saturated aliphatic hydrocarbon can be obtained.

Candle wax: the special wax is used as the base material of various candles and has better hardness and combustion performance.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides candle wax and a preparation method thereof, and high-quality candle wax products can be obtained.

In order to achieve the purpose, the invention adopts the following technical scheme:

a method of making candle wax, comprising:

(1) carrying out catalytic hydrogenation on the Fischer-Tropsch synthesis product to obtain Fischer-Tropsch refined wax;

(2) separating a plurality of narrow fractions with the distillation range of 300-520 ℃ from the Fischer-Tropsch refined wax by distillation;

(3) candle wax is prepared using a narrow cut or a mixture of narrow cuts.

In some embodiments, the distillation mode in step (2) is selected from atmospheric/vacuum rectification, short path molecular distillation, thin film distillation, or any combination thereof.

In some embodiments, the distillation in step (2) is operated at a pressure of from 0.1PaA (absolute) to atmospheric.

In some embodiments, the narrow fraction has a distillation range width of 10-100 ℃, e.g., 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, or 90 ℃.

In some embodiments, in step (3), the narrow fraction or mixture of narrow fractions having a melting point of 30-50 ℃ is used directly as the low melting candle wax.

In some embodiments, in step (3), the high melting candle wax is obtained after de-oiling the narrow fraction or mixture of narrow fractions having melting points of 50-65 ℃.

In some embodiments, in step (3), the manner of de-oiling is fractional crystallization.

In some embodiments, the step of fractional crystallization comprises: crystallizing the narrow fraction at a temperature of 5-10 deg.C below the melting point of the narrow fraction, maintaining the temperature for 1-10h (such as 2h, 3h, 4h, 6h, 8h), and discharging mother liquor residue; then the temperature of the crystal is raised to sweat, and finally the temperature is raised to the melting point; and finally heating the crystal to melt and discharge the material to obtain the candle wax.

In some embodiments, the temperature ramp includes a plurality of temperature gradients.

The candle wax prepared by the preparation method is low-melting-point candle wax or high-melting-point candle wax.

In some embodiments, the low melting candle wax comprises tea wax or cupped wax.

In some embodiments, the high melting point candle wax comprises a dewaxed wax or an LED process wax.

In some embodiments, the high melting candle wax has an oil content of less than 2 weight percent and a penetration @25 ℃ ≦ 25 in 1/10mm units.

Compared with the prior art, the invention has the following beneficial effects:

(1) the invention overcomes the defects of complex composition of petroleum wax, complex candle production process and environmental pollution caused by candle burning, and the adopted coal-based Fischer-Tropsch refined wax becomes an excellent raw material for producing the special wax for the environment-friendly candle because of the characteristics of single group composition, normal paraffin content of more than 90 percent, no impurity, no aromatic hydrocarbon and the like.

(2) The invention carries out full pretreatment and hydrofining on the Fischer-Tropsch synthetic wax, and can improve the quality of target products.

(3) The production method has the advantages of simple process, strong operation flexibility, abundant product types and full utilization of raw materials. The product has stable performance, and the candle special wax obtained by the method is suitable for being used for making various candles and shapes, has good ductility and good applicability to moulds.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.

Some embodiments of the invention use Fischer-Tropsch synthesis products as raw materials, provide a candle wax production method with simple process, and develop tea wax, cup wax and various candle wax products with narrow melting point range, high flash point, stable performance and low cost.

Around the goal, the invention adopts the technical scheme that: the Fischer-Tropsch synthesis product is used as a raw material, and is subjected to hydro-conversion in the presence of a catalyst, so that substances such as oxygen-containing compounds, olefin and the like which are easy to deteriorate in the subsequent high-temperature rectification process, and other impurities such as sulfur, nitrogen and the like which influence the color and taste of the product are removed, and the quality of the product is not influenced. And distilling the hydrogenated product to separate various fractions (C16-C32) with the distillation range of 350-520 ℃, wherein the distillation mode can be one or a combination of several modes of normal pressure/reduced pressure rectification, short-range molecular distillation or thin film distillation and the like, and the mixture of various fractions or any fraction can be further deoiled or directly used as a candle wax product without de-oiling according to the application mode of the candle wax to obtain a series of candle wax products with the flash point of over 160 ℃ and the melting point of 35-60 ℃. The series of products can be applied to various artistic candle formulas, such as canned candles (non-cupped candles), LED artistic candles, various artistic smokeless candles, pollution-free fragrant candles and the like.

For example, in some embodiments, the invention is directed to the specific use of low melting candle wax (e.g., melting point of 35-50 ℃) -tea wax or cupped wax (no-cupped wax), which is separated into narrow fractions by separating light fractions (distillation range of 300-400 ℃), and the narrow fractions or the mixture of any fractions thereof are used for preparing a series of low melting candle waxes without deoiling, so that the production process is simple, the cost is low, and the application of products in the field is satisfied. Meanwhile, aiming at the application fields of high-melting-point candle wax (for example, the melting point is 52-65 ℃) -de-cupped wax, LED process candles and the like, after the 400-through 520 fraction is separated into narrow fractions, fractional crystallization is carried out, the fractional crystallization stages are controlled according to the requirement of the oil content of a target product to complete the de-oiling operation, and finally various process candle wax products are obtained.

Example 1

The Fischer-Tropsch wax is subjected to hydrorefining to obtain Fischer-Tropsch wax, substances such as olefin, oxygen-containing compounds, nitrogen, sulfur and the like which affect the odor, color and the like of products in the Fischer-Tropsch wax are effectively removed, the Fischer-Tropsch wax is subjected to separation by one or a combination of a plurality of modes of a thin film evaporator, a molecular short-path evaporator or a reduced pressure rectifying tower to obtain the effective components of the candelilla wax, wherein the temperature is 300-520 ℃, and the distillation range width of the separated fraction is 10-100 ℃ as required.

Take the processing mode of the thin film evaporator and the short-range evaporator as an example: the pressure of the thin film evaporator is controlled below 50Pa, the pressure of the molecular short path distillation is controlled below 10Pa, and the fractions shown in table 1 are separated:

TABLE 1

Fraction (. degree.C.)	≤350	350-400	400-460	460-520	≥520
						Film temperature (. degree. C.)	170-180
Short range temperature (. degree. C.)		145-160	175-190	225-240

The thin film evaporator is effective in removing light components affecting the flash point and isomeric hydrocarbon components partially affecting the oil content.

Separating Fischer-Tropsch refined wax by a short-range evaporator, wherein the flash point is above 160 ℃, the melting point is 30-50 ℃ for fraction, and the fraction can be directly used as candle wax such as tea wax/non-cup-dropping cup filling wax without deoiling treatment.

The flash point is above 180 ℃, the melting point is 55-65 ℃, the distillate is required to be deoiled, the oil content (solubility in butanone) is below 2 wt%, and the penetration degree is less than or equal to 25(1/10mm) @25 ℃, so that the wax can be used as the candle wax such as cupped filling wax, LED process electronic candle and the like.

In the embodiment of the invention, the wax for candlepower is deoiled in a fractional crystallization mode, the fractional crystallization is completed in four different treatment stages, the first treatment stage is cooling/crystallization, and nucleation of crystals is formed on the surface of a crystallizer. The second stage is thermostatted at the temperature of the first stage for a period of time to allow crystals to grow together and form a solid on the cooled surface. At the bottom of the crystallizer, the residual liquid portion of the feed is discharged by opening the bottom valve. In the third stage, the temperature is slowly raised, sweating occurs on the surface of the solid wax, and the isomeric components and light components are discharged. And finally, waxing the cooling plate, heating to melt and discharging. The wax product from the crystallizer has a lower oil content (solubility in butanone) and penetration than the feed.

For example, in the embodiment, the 400-460 ℃ fraction is melted at the melting point of 59.1 ℃ and then is subjected to fractional crystallization, cooling/crystallization is carried out at the temperature of 5-10 ℃ lower than the melting point, the temperature is kept constant for more than 4 hours at the temperature, mother liquor residue is discharged, and the residue accounts for 20-80% of the raw materials; and then the crystal is heated to sweat, in order to effectively improve the product quality, the sweating process can be divided into a plurality of temperature gradients, and the temperature gradient is finally raised to be near the melting point, so that the sweating product accounts for 20-50% of the crystal, and finally the crystal is heated, melted and discharged to be used as a candle wax product. According to the requirement of the oil content of the target product, secondary crystallization treatment can be carried out according to the change of the melting point to obtain the final target product, and the experimental period is 36-48 h. The properties of the target product are shown in table 2.

TABLE 2

Comparative example 1

In the comparative example, hydrofining and deoiling operations are sequentially carried out on the coal-based Fischer-Tropsch synthetic wax to obtain deoiled Fischer-Tropsch refined wax, and then short-path distillation is carried out to obtain narrow-fraction components after fractionation; and (3) sweating and deoiling the target fraction or narrow fraction blending component, and controlling the sweating temperature according to the melting point requirement of the product to obtain the candle wax product.

The 400-DEG C460-DEG C fraction is treated by a sweating process, sweating is carried out after melting and solidification, the temperature is divided into a plurality of temperature gradients, the temperature is finally increased to be near the melting point, the final product accounts for 56 percent of the raw material and is used as a candle wax product, the oil content of the product is reduced to 1 percent, and the experimental period is 60-72 hours.

Therefore, the invention can obviously shorten the experimental period and improve the production efficiency.

The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.