WO2011011972A1 - 一种提取褐煤蜡的方法 - Google Patents

一种提取褐煤蜡的方法 Download PDF

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Publication number
WO2011011972A1
WO2011011972A1 PCT/CN2010/001140 CN2010001140W WO2011011972A1 WO 2011011972 A1 WO2011011972 A1 WO 2011011972A1 CN 2010001140 W CN2010001140 W CN 2010001140W WO 2011011972 A1 WO2011011972 A1 WO 2011011972A1
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Prior art keywords
coal
solvent
montan wax
wax
semi
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PCT/CN2010/001140
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English (en)
French (fr)
Inventor
谷俊杰
宋成才
张力隽
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新奥科技发展有限公司
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Priority to AU2010278595A priority Critical patent/AU2010278595B2/en
Publication of WO2011011972A1 publication Critical patent/WO2011011972A1/zh

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Classifications

    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0203—Solvent extraction of solids with a supercritical fluid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0288—Applications, solvents
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
    • 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
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/44—Solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • a method of extracting montan wax is a rare mineral present in lignite, a mixture comprising wax, resin and asphalt.
  • the nature of the montan wax depends primarily on the starting material, the solvent used and the leaching conditions.
  • the color of the asphalt increases from brown to black. Melting point
  • the main components of the wax are: wax esters composed of C16 C34 acid and C24, C26, C30 alcohols; long-chain fatty acids (C16 ⁇ C35); fatty alcohols (C20 ⁇ C34) and anthracene hydrocarbons (C23 - C33).
  • the components of the resin are resin acids, small amounts of sterols and terpenes. Bitumin is primarily a polymeric, esterified oxygenated resin acid. Because of its high hardness, high melting point and stable chemical properties, montan wax is widely used in daily chemical, precision casting, papermaking, printing, textile and other industries.
  • montan wax is mainly extracted from lignite, and the extraction technology is mainly extracted directly from lignite.
  • the solvents used are mainly benzene, toluene, solvent oil and the like.
  • China's lignite wax resources are relatively scarce.
  • the content of montan wax is low, and some wax sources are nearly exhausted after years of mining.
  • Other coal types also contain a certain amount of montan wax, but the content is low and the extraction cost is large. Therefore, the lignite wax is still mainly extracted from lignite in industrial production.
  • the method for extracting lignite wax from abroad is as follows: First, the raw material lignite is dried, and the lignite is first passed through a rotating inclined drum dryer, dried to a moisture content of 15-20%, and then the lignite is ground and ground to a particle size. Less than 1. 3mm, and then dried.
  • the pulverized coal was added to a continuous leaching machine, and the lignite was leached by using toluene as a solvent at a temperature of 82 °C.
  • the waxy leach solution is sent to an evaporative separator, and fractionated at 125 to 130 ° C.
  • the distilled toluene is recycled, and the remaining crude wax liquid is cooled and formed into a coarse brown coal wax.
  • the coarse brown coal wax contains 7 to 10% of asphalt and 18 to 20% of resin.
  • the main part of the leacher is a rotatable conveyor belt with several hoppers.
  • the hopper first receives a certain amount of coal.
  • the toluene solvent is sprayed into the running hopper.
  • the coal contained in the hopper is leached, and the immersed wax-containing leaching liquid flows out from the sieve plate at the bottom of the hopper, and then Enter the distillation system and other auxiliary systems to separate the wax from the solvent.
  • the domestic method for extracting montan wax is as follows: The lignite is pulverized to a particle size of 3 to 10 mm, dried to about 20% of water, placed in a leaching device, and a certain amount of pure benzene (about 8 times of the raw coal) is added. Stay in the leacher for about 2 to 4 hours. In order to enhance the operating conditions, increase the leaching rate, and shorten the leaching time, it is usually immersed by a slight pressure to bring the solvent (benzene) to a boiling point of 90 °C. After leaching, the material was filtered, and the filtrate was passed to an evaporator and heated by evaporation with water vapor.
  • the low boiling point of benzene (boiling point of benzene at atmospheric pressure is 80 ° C) and water escape as vapor, and after condensation at the top of the evaporator through the condenser, it enters the oil-water separator, and lignite wax is obtained at the bottom of the evaporator.
  • the lignite must be dried before leaching so that the moisture content of the coal is less than 20%;
  • Benzene and benzene are strongly toxic substances, which may cause harm to operators or cause pollution to the surrounding environment;
  • Chinese patent CN101029255 describes a method for extracting brown coal by using a mixture of alcohol and cyclohexane, the particle size of the coal particles is 0. 6 ⁇ 20 let, the leaching method is intermittent leaching in the leaching device, solid-liquid volume The ratio is 1:1 ⁇ 1: 4, and the solution after leaching is subjected to solvent recovery, and the obtained product is montan wax.
  • the patent uses a less toxic solvent, it still needs to use lignite with a certain wax content as a raw material, and can not get rid of the limitation of raw materials, and the process needs to separate the extracting agent and then mix it in proportion, which not only increases The complexity of the process increases the energy consumption, equipment investment and manpower input. Summary of invention
  • the present invention provides a method for extracting montan wax from coal. Specifically, the present invention relates to a method for pretreating coal by a subcritical or supercritical fluid and then leaching the montan wax with a solvent, the method comprising the steps of:
  • the present invention also provides a method of extracting montan wax, comprising the steps of:
  • the coal ash may optionally be mixed with water in any manner known in the art to prepare a coal water slurry.
  • the coal may be selected from the group consisting of bituminous coal, anthracite, lignite, and mixtures thereof. It is particularly noted that coals which are not treated by conventional solvent leaching due to low montan wax content are also suitable as raw materials for the present invention.
  • the pulverized coal has a particle size of less than 300 microns, preferably from 60 to 150 microns.
  • the content of pulverized coal may be from 8 to 68% by weight, preferably from 25 to 45% by weight, based on the total weight of the coal water slurry.
  • a certain amount of catalyst is added to the coal water slurry.
  • the catalyst is selected from the group consisting of alkali metal or alkaline earth metal oxides, alkali metal or alkaline earth metal hydroxides and alkali metal or alkaline earth metal salts, or mixtures thereof, for example selected from the group consisting of K 2 O, Na 2 0, Ca 0, Mg 0, MN, NaOH. And Ca(0H) 2 , Mg(0H) 2 , K 2 C0 3 or Na 2 C0 3 or the like, or a mixture thereof, is added in an amount of 3 to 30 wt%, preferably 5 to 10 wt%, of the coal powder.
  • the above prepared coal water slurry is fed into the reactor by a fluid delivery device such as a pump to perform step a).
  • high temperature and high pressure water is added to the reactor to adjust the ratio of coal to water in the reactor.
  • the ratio of coal to water in the counter can be 1:1-1:20, preferably 1:1-1:5 .
  • the coal water slurry may be first mixed with the high temperature and high pressure water and then the mixture is fed to the reactor.
  • the water in the reactor is in a subcritical state or a supercritical state, wherein the subcritical state of the water is 10-22 MPa (the pressures used herein are absolute pressures) and 120-374 ° C, and the supercritical state of the water is 22. l-30MPa and 374-650 ⁇ .
  • the state of the water in the reactor is preferably a pressure of 15 to 25 MPa and a temperature of 300 to 500 °C. After the reaction conditions are reached, the reaction is carried out for 1 to 30 minutes, preferably for 5 to 10 minutes. After the end of the reaction, separation is carried out in any conventional separation to give a solid product, a gas product, and a light tar.
  • the solid product is semi-coke, which contains montan wax, and the solid product may be impregnated with normal temperature and normal pressure deionized water to dissolve the catalyst therein.
  • the small amount of phenolic substances contained in the coal and the methane-rich gas produced by the treatment of the coal are mixed and dissolved in the subcritical or supercritical fluid.
  • phenols are recovered and sold as products, which are rich in methane.
  • the gas can be further purified and used as a fuel gas.
  • the process of extracting these phenolic materials and methane-rich gas from coal with supercritical fluid or subcritical fluid and leaving the semi-coke containing montan wax is generally referred to as the "peeling" process of coal.
  • the inventors have also found that by selecting the specific type and/or composition of the above catalyst, it is possible to control the degree of exfoliation of coal in step a) and also to control the amount of montan wax extracted in the subsequent step b). And purity.
  • the main components of the semi-coke are carbon, ash and volatile matter, and have the characteristics of color black porosity, large porosity and low mechanical strength.
  • the semi-coke high porosity characteristics greatly increase its contact surface area with the solvent, which is ideal for solvent leaching, and the components in the coal are treated by subcritical or supercritical fluids.
  • the complex reaction produces wax components that contribute to wax yield and quality. Need to refer It is to be noted that the fluid used in the step a) is not limited to water, and other fluids such as alcohols or carbon dioxide may also be used.
  • the fluid temperature and pressure of the selected fluid For the particular temperature and pressure of the selected fluid, those skilled in the art will be able to determine whether it is within the temperature and pressure ranges corresponding to the supercritical and subcritical states based on its critical temperature and critical pressure and conventional technical practice. For example, if the fluid temperature is above the critical temperature and the fluid pressure is above the critical pressure, the fluid is said to be in a supercritical state; the definition of the subcritical state is more complicated, even for the same fluid, different documents are defined as different Temperature range and pressure range.
  • the definition of the subcritical state follows the range given, and if a clear temperature range and pressure range are not given, The definition of the subcritical state follows the following principles: If the fluid temperature is above its normal pressure boiling point and below its critical temperature and the fluid pressure is the pressure that keeps the fluid liquid, the fluid is said to be in a subcritical state.
  • the lignite wax may be leached from the semi-coke using a solvent capable of dissolving the montan wax as a leaching solvent.
  • the solvent may be any solvent in the art, including but not limited to: an aqueous solution of an alcohol, a mixture of an alcohol and a hydrocarbon solvent, a ketone solvent or an ether solvent, etc., wherein the hydrocarbon solvent may be selected from the group consisting of benzene and toluene. N-hexane, cyclohexane, mineral spirits or a mixture thereof. Mixtures of various solvents can also be used.
  • the alcohol is preferably selected from the group consisting of methanol, ethanol, isopropanol, propylene glycol or a mixture thereof.
  • the volume of the alcohol in the mixture may be from 30 to 99% by volume.
  • an aqueous solution of an alcohol is used, the volume of the alcohol in the aqueous solution may be from 30 to 99%.
  • the immersion conditions of the step b) are: a temperature of 65-200 ° C and a pressure of 0. l-lMPa.
  • the leaching can be carried out batchwise or continuously.
  • the semi-coke is immersed in the leaching solvent, and after a certain period of time, the solid-liquid separation is carried out, and the solid remaining after the solvent recovery of the liquid phase is coarse brown coal wax, and further refined to obtain fine Brown coal wax.
  • a certain size of semi-coke can be sent from the hopper to the conveying device of the continuous leaching device, and the leaching solvent is sprayed on the semi-coke powder for leaching, and the leaching liquid is passed through the conveying device.
  • the sieve hole leaks into the storage tank of the leaching device, and then the residual semi-coke is removed by filtration, and the water which may be caused by the solvent is removed by oil-water separation, and the removed water can be recycled to the pulping step for reuse, and then passed.
  • the solvent in the oil phase product is removed by flash evaporation, distillation, etc., and dried to obtain a dried montan wax product.
  • the removed solvent can also be collected and reused.
  • the remaining lignite is greatly improved in purity and can be sold as a upgraded lignite product.
  • a semi-coke pretreatment step may optionally be added between step a) and step b), the semi-coke being carried out under the addition of water, hydrogen, carbon dioxide or the like or a combination thereof. Pretreatment to increase the leaching rate in step b).
  • step a a certain amount of hydrogen is added to the reactor to modify the coal to further increase the content of montan wax in the coal, thereby obtaining a second type of embodiment of the present invention.
  • the particle size of coal powder, the ratio of water to coal, the selection of catalyst, the amount of addition, the selection of coal, the state of supercritical water, the reaction temperature, the pressure, etc. are selected as the above first embodiment.
  • hydrogen gas is added to the system through a gas compressor, so that the partial pressure of hydrogen in the system reaches 1 - 5 MPa.
  • the present invention has significant advantages over conventional methods. Firstly, since the present invention does not directly immerse the lignite powder, the raw material is first converted into a semi-coke by subcritical fluid or supercritical fluid treatment, thereby greatly increasing the contact area between the raw material and the solvent, thereby improving the leaching rate. Therefore, the raw material of the present invention is not limited to lignite, but any coal containing montan wax component can be used, especially lignite which cannot be utilized in the conventional method. Coal with low wax content can even use gasification residual coke of coal such as bituminous coal, which expands the source of raw materials and reduces costs.
  • the solvent used in the invention is widely used, the price is lower than that of the conventional solvent, and the toxicity is small, the damage is not caused to the operator, and the solvent is volatilized and diffused into the air to pollute the environment, and is an environmentally friendly solvent.
  • the type and/or composition of the catalyst it is possible to control the amount of leaching and purity of the montan wax, which reduces the amount of work required to purify the coarse brown coal wax in the subsequent steps.
  • the process of the present invention also produces methane-rich gas, small amounts of phenols, and upgraded lignite, which can be sold as products to further enhance the economics of the process of the present invention.
  • Figure 1 is a schematic flow diagram of an embodiment of the present invention.
  • the lignite raw coal pulverized coal having a particle size of 60 - 150 ⁇ m is crushed and sieved to prepare 3 Owt% of coal water slurry, which is mixed with water reaching subcritical or supercritical state, and then added to the reactor. Without adding any catalyst, the temperature and pressure of the reactor are as shown in Table 1. Under these conditions, the coal is treated to produce a mixture containing decane, a mixture of fuel and water, a combustible solid component, a gas, After the liquid and solid three phases are separated in the separator, the obtained solid matter is cooled to a semi-coke.
  • the semi-coke obtained as above is crushed, sieved and then enters the coal storage tank, and sent to the conveyor in the leaching device by the coal hopper, the ethanol-water mixed solvent having a temperature of 100 'C and an ethanol volume content of 50% is dipped
  • the upper part of the extractor is sprayed on the semi-coke powder, and the leachate is leaked through the sieve hole of the conveyor to the storage tank in the lower part of the leaching device.
  • the leaching device The internal pressure is 0.15 MPa; the liquid outlet of the lower tank of the leaching device is opened every 20 minutes, the leaching liquid passes through the filter, and a small amount of semi-coke solid mixed in the leaching liquid is filtered, and the liquid phase enters.
  • the oil-water separation is carried out, and the upper waxy liquid phase obtained after the oil-water separation is introduced into the flash tank for solvent recovery, and the recovered solvent can be returned to the leaching device for recycling, and the still in the flash tank
  • the leachate containing a certain amount of solvent is dried in a wax dryer to obtain a product montan wax; the lower aqueous phase of the oil-water separation tank is recovered by salt removal, and then reused.
  • the lignite raw coal pulverized coal having a particle diameter of 60 to 150 ⁇ m was crushed and sieved to make 30 wt. /.
  • the coal water slurry, and adding the catalyst K 2 C0 3 with a weight of 5% of the coal powder, the coal water slurry is mixed with the water reaching the subcritical or supercritical state, and then added to the reactor, the temperature and pressure of the reactor are as follows. As shown in Table 1, the coal is treated under this condition to produce a mixture of methane, a mixture of fuel and water, a combustible solid component, and a gas, a liquid, and a solid three phase separated in a separator. The solid matter is semi-coke after cooling.
  • the extraction solvent was changed to an ethanol-cyclohexane mixed solvent having an ethanol volume of 35%, and the coal type, catalyst, other parameters and process conditions were the same as in Example 1.
  • the lignite raw coal pulverized coal having a particle size of 60 - 150 ⁇ m is crushed and sieved to make 30 wt% of coal water slurry, and the catalyst K 2 C0 3 having a weight of 5% by mass of coal powder is added. After the slurry is mixed with the water that reaches the subcritical or supercritical state, it is added to the reactor, and hydrogen is added to the system through the gas compressor to make the partial pressure of hydrogen in the system reach
  • step b) of leaching the lignite coal powder was carried out directly using the same solvent and leaching conditions as in Example 1, without carrying out step a).
  • step b) of leaching the lignite coal powder was carried out directly using the same solvent and leaching conditions as in Example 3, without carrying out step a).
  • the coal type used is bituminous coal, and the treatment method and process parameters are exactly the same as those in the third embodiment.
  • step b) of leaching the bituminous coal powder was carried out directly using the same solvent and leaching conditions as in Example 5, without carrying out step a).
  • step a) and step b) of embodiment 1 a step of pretreating the semi-coke with hydrogen is introduced, the semi-coke pretreatment step being independent of the steps of step a) and step b), in FIG.
  • the separator shown is followed by and before step b).
  • the semi-coke pretreatment method is: adding a ratio of 1000 m 3 of hydrogen per ton of semi-coke to a fixed bed reactor, heating to 400 ° C, maintaining for 5 minutes, cooling, and performing step b of Example 1 on the solid obtained by the reaction. .
  • the process conditions and results of the above respective examples and comparative examples are shown in Table 1.
  • the wax yield is only 1. 45% and 1.78%, see Comparative Example 2 and Comparative Example 3, and the wax yield after the treatment of step a) is 2 .28°/. And 3. 51%, see Example 1 and Example 3.
  • hydrogen is introduced in step a)
  • the wax yield is further increased, see Example 4.
  • bituminous coal is used as the raw material, if the solvent is directly leached without any treatment, almost no substance which is characteristic of montan wax is detected (see Comparative Example 4), and after the treatment of step a), the wax yield can reach 1. 75% (see Example 5).
  • Example 6 is a step of pretreating the semi-coke with hydrogen between steps a and b. From the results, the wax yield is further compared with the example 1 of steps a and b under the same conditions only. improve. When the other parts were the same, the addition of the catalyst was obviously higher than that of the catalyst without the catalyst, see the comparison of Example 1 and Comparative Example 1. When the composite catalyst of the two carbonates is used, the wax yield is higher than that of the single carbonate as the catalyst, as shown in Example 2 and Example 1, and the lignite wax obtained in Example 2 was visually observed by the inspectors. Its color is closer to the color of pure lignite wax than the lignite wax obtained in Example 1, which proves that the former is more pure.
  • the wax yield refers to the mass percentage of the obtained lignite wax to the raw coal.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Solid Fuels And Fuel-Associated Substances (AREA)
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Description

一种提取褐煤蜡的方法 褐煤蜡是存在于褐煤中的稀有矿产， 是一种包含蜡、 树脂和 地沥青的混合物。 褐煤蜡的性质主要取决于原料、 所采用的溶剂 和浸取条件。 随地沥青含量的增加， 其颜色由棕色至黑色。 熔点
75 ~ 86 °C , 密度（ 20°C ) 0· 98 ~ 1. 03g/cm3。 蜡的主要成分为： 由 C16 C34酸和 C24、 C26、 C30醇组成的蜡酯； 长链脂肪酸（C16 ~ C35)； 脂肪醇（C20 ~ C34)和垸烃（C23 - C33)。 树脂的成分是树脂 酸， 少量甾醇和萜烯类物质。 地沥青主要是聚合的、 酯化的含氧 树脂酸。 由于褐煤蜡的硬度大、 溶点高、 化学性质稳定， 其广泛 应用于日用化工、 精密铸造、 造纸、 印刷、 纺织等工业。 目前褐 煤蜡主要从褐煤中提取， 提取技术主要直接从褐煤中提取， 所采 用的溶剂主要有苯、 曱苯、 溶剂油等。 但我国的褐煤蜡资源相对 匮乏， 总体来说褐煤蜡含量偏低， 有的蜡源经过多年的开采已经 接近枯竭。 其它煤种中也含有一定量的褐煤蜡， 但含量偏低， 提 取成本大， 故目前工业生产中仍主要从褐煤中提取褐煤蜡。
国外对褐煤蜡的提取方法是： 先对原料褐煤进行干燥， 将褐 煤先经过转动的倾斜转筒式干燥器， 千燥到含水分 15 ~ 20%， 再 将褐煤磨碎、 磨细到粒径小于 1. 3mm、 再干燥。 将煤粉加入到连 续浸取器中， 在 82 °C温度下， 用甲苯作溶剂， 对褐煤进行浸取。 得到含蜡浸取液送入蒸发分离器， 在 125 ~ 130°C下进行分馏， 蒸 馏出来的甲苯循环使用，余下的粗蜡液冷却成型， 即为粗褐煤蜡。 粗褐煤蜡含沥青 7 ~ 10%, 树脂 18 ~ 20%。 浸取器的主要部分是一 个可转动的带若干料斗的运输带。 料斗先接受一定量的煤， 在料 斗传动过程中， 甲苯溶剂喷淋在正在运行的料斗内。 对料斗内装 的煤进行浸取， 浸取后的含蜡浸取液， 由料斗底部筛板流出， 再 进入蒸馏系统及其它辅助系统进行蜡与溶剂的分离。
国内提取褐煤蜡的方法为： 将褐煤粉碎到粒度为 3 ~ 10mm， 干燥到含水 20%左右， 置于浸取器中， 加入一定量的纯苯（约为原 料煤的 8倍）， 煤在浸取器中停留约 2 ~ 4小时。 为了强化操作条 件， 提高浸取率， 缩短浸取时间， 通常稍加一些压力使溶剂（苯） 沸点达到 90°C进行浸取。 浸取后将物料过滤， 滤液进入蒸发器， 用水蒸气加热蒸发。 低沸点的苯（常压下苯的沸点为 80°C)和水以 蒸气形式逸出, 并在蒸发器顶部经冷凝器冷凝后进入到油水分离 器， 而在蒸发器的底部得到褐煤蜡。
但目前的褐煤蜡提取技术存在的主要问题有：
( 1 )原料资源受限， 必须釆用褐煤原煤；
( 2 )浸取前必须对褐煤进行干燥，使煤的水分含量低于 20%;
( 3 ) 煤的粒径较大， 在 600 微米以上， 或者使用 3 ~ 10mm 的块状煤， 不利于完全有效的浸取；
( 4 )苯、 曱苯为强烈毒性物质， 容易对操作者造成危害或对 周围环境造成污染；
( 5 )提取蜡后的残渣中仍混有大量的溶剂未进行回收， 不仅 造成溶剂的损失， 残留在褐煤蜡中的溶剂限制了产品的使用。
中国专利 CN101029255介绍一种采用醇和环己烷的混合物对 褐煤进行提取的方法， 煤粒的粒径为 0. 6 ~ 20讓， 浸取方式为在 浸取器中进行间歇浸取， 固液体积比为 1： 1 ~ 1： 4， 浸取后的溶液 进行溶剂回收， 得到的产品为褐煤蜡。 该专利虽然该用了毒性较 低的溶剂， 但仍需要以有一定含蜡量的褐煤为原料， 不能摆脱原 料的限制， 而且该工艺需要将萃取剂分离后再按比例进行混合， 不仅增加了工艺的复杂性， 而且增加了能源的消耗、 设备的投资 以及人力投入。 发明概述
本发明提供了一种从煤中提取褐煤蜡的方法， 具体地， 本发 明涉及通过亚临界或超临界流体对煤进行预处理， 然后用溶剂浸 取褐煤蜡的方法， 该方法包括以下步骤：
a) 将煤粉在催化剂作用下在亚临界或超临界流体中进行处 理， 得到含有褐煤蜡的半焦；
b)用能够溶解所述褐煤蜡的溶剂将所述褐煤蜡从所述半焦中 浸取出来。
本发明的步骤 a ) 中还可以加入氢气。 因此， 本发明还提供 了提取褐煤蜡的方法， 包括以下步骤：
a)将煤粉在催化剂和氢气的作用下在亚临界或超临界流体中 进行处理， 得到含有褐煤蜡的半焦；
b)用能够溶解所述褐煤蜡的溶剂将所述褐煤蜡从所述半焦中 浸取出来。
发明详述
其中， 在 a ) 步骤之前， 可以任选地以任何本领域已知的方 式将煤粉与水混合制备水煤浆。 其中煤可以选自烟煤、 无烟煤、 褐煤及它们的混合物， 特别需要指出的是， 那些由于褐煤蜡含量 低而无法用传统溶剂浸取法处理的煤也适合作为本发明的原料。 煤粉的粒度小于 300微米，优选为 60- 150微米。 以水煤浆总重量 计， 煤粉的含量可以为 8- 68wt % , 优选 25- 45wt %。 在水煤浆中 加入一定量的催化剂。 催化剂选自碱金属或碱土金属氧化物、 碱 金属或碱土金属氢氧化物和碱金属或碱土金属盐， 或它们的混合 物， 例如选自 K20、 Na20、 Ca0、 Mg0、丽、 NaOH、 Ca (0H) 2、 Mg (0H) 2、 K2C03或 Na2C03等， 或它们的混合物， 催化剂加入量为煤粉的 3-30wt , 优选 5-10wt%。 以上配制的水煤浆以流体输送设备例如泵送入反应器中以执 行步骤 a ) 。 同时向该反应器中加入高温高压水， 以调节反应器 中的煤与水的比例， 例如反症器中的煤水比例可为 1 : 1-1: 20， 优选 1 : 1-1: 5。 或者， 水煤浆也可以先与所述高温高压水进行混 合然后将混合物进料到反应器中。 使反应器中的水处于亚临界状 态或超临界状态， 其中水的亚临界状态为 10- 22MPa (本文中使用 的压力均为绝对压力） 和 120-374 °C， 和水的超临界状态为 22. l-30MPa 和 374- 650 Ό。 反应器中水的状态优选为压力 15-25MPa 和温度 300- 500°C。 达到反应条件后， 反应进行 1-30 分钟， 优选 5-10分钟。 反应结束后， 以任何常规分离方式进行分 离得到固体产物、 气体产物和轻质焦油。其中固体产物即为半焦， 其中含有褐煤蜡， 可用常温常压去离子水对该固体产物进行浸渍 以溶解出其中的催化剂。 而煤中所含的少量酚类物质和煤经处理 而产生的富含甲烷的气体则混溶于亚临界或超临界流体中带走， 这些酚类被回收后可作为产品出售， 富含甲烷的气体则可进一步 净化后作为燃料气使用。 本领域中， 通常将用超临界流体或亚临 界流体从煤中提取这些酚类物质和富含甲烷的气体并剩下含有褐 煤蜡的半焦的过程称为煤的 "剥离" 过程。 此外， 发明人还发现， 通过对上述催化剂的具体种类和 /或组成进行选择，能够控制步骤 a ) 中的对煤的剥离程度， 且还能控制后续步骤 b ) 中被萃取的褐 煤蜡的量以及纯度。
该半焦的主要成分是碳、 灰分和挥发分， 具有色黑多孔、 孔 隙率大而机械强度低的特点。 与煤粉相比， 半焦高孔隙率的特征 大大增加了其与溶剂的接触表面积， 这对于溶剂浸取来说是非常 理想的， 而且煤中成分经过亚临界或超临界流体处理后， 经过复 杂的反应， 生成蜡的成分， 有利于蜡产率和品质的提高。 需要指 出的是， 步骤 a ) 中所用的流体并不限于水， 也可以使用其它流 体， 例如醇类或二氧化碳等。 对于所选择的流体的具体温度和压 力来说， 本领域技术人员能够根据其临界温度和临界压力和常规 技术实践来判断其是否处于超临界和亚临界状态所对应的温度和 压力范围之内。 例如， 若流体温度高于临界温度且流体压力高于 临界压力， 则称该流体处于超临界状态； 而亚临界状态的定义则 比较复杂， 即便是对相同的流体， 不同的文献也定义为不同的温 度范围和压力范围。 为了清楚起见， 在本文中， 若已经给出亚临 界状态的明确的温度范围和压力范围， 则亚临界状态的定义遵从 所给出的范围， 若没有给出明确的温度范围和压力范围， 则亚临 界状态的定义遵从以下原则： 若流体温度在其常压沸点以上且在 其临界温度以下而流体压力为使该流体保持为液态的压力， 则称 该流体处于亚临界状态。
在步骤 b)中， 可以用能够溶解褐煤蜡的溶剂作为浸取溶剂来 从半焦中浸取褐煤蜡。 该浸取步骤在浸取器中进行。 所述溶剂可 以采用本领域的任何溶剂， 包括但不限于： 醇的水溶液、 醇与烃 类溶剂的混合物、 酮类溶剂或醚类溶剂等， 其中所述烃类溶剂可 选自苯、 甲苯、 正己烷、 环己烷、 溶剂油或它们的混合物。 也可 以使用各种溶剂的混合物。 其中所述醇优选选自甲醇、 乙醇、 异 丙醇、 丙二醇或它们的混合物。 当使用醇与烃类溶剂的混合物时， 醇在该混合物中的体积含量可为 30-99 %。 当使用醇的水溶液时， 醇在该水溶液中的体积含量可为 30-99 %。步錄 b )的浸取条件是： 温度为 65-200°C , 压力为 0. l-lMPa。
浸取可以间歇进行或连续进行。 在间歇浸取方法中， 将半焦 浸入浸取溶剂中， 一定时间后， 进行固液分离， 对液相进行溶剂 回收后所剩余的固体即为粗褐煤蜡， 进行进一步精制后可得到精 褐煤蜡。
在连续浸取方法中， 可以将一定粒度的半焦由加料斗送至连 续浸取装置的传送装置上， 使浸取溶剂淋洒在半焦粉末上进行浸 取， 浸取液通过传送装置上的筛孔漏到浸取器的储罐中， 然后通 过过滤除去残留的半焦，通过油水分离除去可能随溶剂带来的水， 所除去的水可以循环到制浆步驟中回用， 然后通过闪蒸、 蒸馏等 技术除去油相产物中的溶剂， 并经干燥得到千燥的褐煤蜡产品。 所除去的溶剂也可以收集回用。
在从半焦中浸取出褐煤蜡之后， 剩下的褐煤因纯净度大大提 高， 可作为提质的褐煤产品出售。
或者， 在某些情况下， 可以任选地在步骤 a )和步骤 b )之间 增加一个半焦预处理步骤， 对半焦在加入水、 氢气、 二氧化碳等 物质或其组合的奈件下进行预处理， 以提高步骤 b ) 中的浸取率。
以上是本发明的第一类实施方案。 本发明还可以以其它的方 式实施。 例如在上述步骤 a)中， 向反应器中加入一定量的氢气， 对煤进行改性处理， 以进一步提高煤中褐煤蜡的含量， 由此得到 本发明的第二类实施方案。在该笫二类实施方案中， 煤粉的粒度、 水煤比例、 催化剂的选择、 添加量、 煤的选取、 超临界水的状态、 反应温度、 压力等参数的选取如以上第一类实施方式中所述， 而 步骤 a ) 中通过气体压缩机向系统中加入氢气， 使系统中的氢气 分压达到 1 - 5MPa。
与传统方法相比， 本发明具有显著的优点。 首先， 由于本发 明并不直接浸取褐煤粉， 而是先将原料进行亚临界流体或超临界 流体处理转化为多孔的半焦，大大提高了原料与溶剂的接触面积， 进而提高了浸取率， 因此本发明的原料不仅限于褐煤， 而是可以 使用任何含褐煤蜡成分的煤， 尤其是传统方法中无法利用的褐煤 蜡含量低的煤， 甚至也可以使用烟煤等煤种的气化残焦， 这扩展 了原料来源， 也降低了成本。 其次， 本发明采用的溶剂来源广泛、 价格较传统溶剂低，且毒性很小，基本不会对操作人员造成伤害， 也不会由于溶剂挥发扩散到空气中污染环境， 属于环境友好型溶 剂。 笫三.， 通过控制催化剂的种类和 /或组成， 能够控制褐煤蜡的 浸取量以及纯度， 这减少了后续步骤对粗褐煤蜡提纯的工作量。 第四， 本发明的方法还副产富含甲烷的气体、 少量酚类以及提质 后的褐煤， 这些副产物均可作为产品出售， 进一步提高本发明的 工艺的经济效益。 附图简述
图 1是本发明的实施方案流程示意图。
实施例
结合附图 1 通过以下非限制性的实施例来说明本发明的方 法。
对比例 1
将经破碎并筛分到粒径为 60 - 150微米的褐煤原煤煤粉制成 3 Owt%的水煤浆， 该水煤浆与达到亚临界或超临界状态的水混合 后， 加入反应器中， 不加入任何催化剂， 反应器的温度和压力如 表 1所示， 在此条件下对煤进行处理， 产生含曱烷的混合气、 可 燃油分和水的混合物、 可燃固体成分， 将气体、 液体、 固体三相 在分离器中分离后， 得到的固体物质冷却后即为半焦。
如上得到的半焦经破碎、 筛分后进入贮煤罐， 经加煤斗送至 浸取器中的传送装置，温度为 100 'C且乙醇体积含量为 50%的乙醇 -水混合溶剂从浸取器上部喷洒在半焦粉末上， 浸取液通过传送 带的筛孔漏至浸取器下部的储罐中。 为保证溶剂的液相， 浸取器 内的压力为 0. 15MPa;每隔 20分钟打开浸取器下部储罐的出液口， 浸取液经过过滤器， 过滤掉浸取液中混有的少量半焦固体后， 液 相进入到分液器中， 进行油水分离， 油水分离后得到的上层含蜡 液相进入闪蒸罐， 进行溶剂回收， 回收的溶剂可以返回加入到浸 取器中进行回收再利用， 闪蒸罐中的仍含有一定量溶剂的浸取物 进入蜡干燥器进行干燥， 得到产品褐煤蜡； 油水分离罐的下层水 相经除盐等处理后回收再利用。
实施例 1
将经破碎并筛分到粒径为 60 - 150微米的褐煤原煤煤粉制成 30wt。/。的水煤浆， 并加入重量为煤粉质量 5%的催化剂 K2C03， 该水 煤浆与达到亚临界或超临界状态的水混合后， 加入反应器中， 反 应器的温度和压力如表 1所示， 在此条件下对煤进行处理， 产生 含甲烷的混合气、 可燃油分和水的混合物、 可燃固体成分， 将气 体、 液体、 固体三相在分离器中分离后， 得到的固体物质冷却后 即为半焦。
后面的浸取步骤和参数与对比例 1相同。
实施例 2
该实施例的步驟与实施例 1 基本相同， 不同之处仅在于用 K2C03: Na2C03=l: 1 (重量比）的混合物来代替纯 K2C03, 总催化剂使 用量仍为煤粉质量 5%。
实施例 3
将萃取溶剂改为乙醇体积含量为 35%的乙醇-环已烷混合溶 剂， 煤种、 催化剂、 其它参数及工艺条件均与实施例 1相同。
实施例 4
将经破碎并筛分到粒径为 60 - 150微米的褐煤原煤煤粉制成 30wt%的水煤浆， 加入重量为煤粉质量 5%的催化剂 K2C03, 该水煤 浆与达到亚临界或超临界状态的水混合后， 加入反应器中， 同时 通过气体压缩机向系统中加入氢气， 使系统中的氢气分压达到
5MPa, 其它工艺步骤和参数均与实施例 1相同。
对比例 2
采用与实施例 1相同的溶剂和浸取条件直接进行对褐煤煤粉 进行浸取的步骤 b) , 而不进行步驟 a) 。
对比例 3
采用与实施例 3相同的溶剂和浸取条件直接进行对褐煤煤粉 进行浸取的步骤 b) , 而不进行步驟 a) 。
实施例 5
采用的煤种为烟煤原煤， 其处理方法及工艺参数与实施例 3 完全相同。
对比例 4
采用与实施例 5相同的溶剂和浸取条件直接进行对烟煤煤粉 进行浸取的步骤 b) ， 而不进行步骤 a) 。
实施例 6
在实施例 1的步骤 a)和步骤 b)中间加入一个通入氢气对半 焦进行预处理的步骤， 该半焦预处理步驟是独立于步骤 a) 和步 骤 b)的步骤， 在图 1中所示的分离器之后且在步驟 b)之前。 该 半焦预处理方法为： 以每吨半焦加入 1000m3氢气的比例加入固定 床反应器， 加热到 400°C， 维持 5分钟， 降温， 对反应得到的固 体实施实施例 1的步驟 b) 。 以上各实施例和对比例的工艺条件和结果见表 1。 由表 1的数据可看出， 相同的褐煤原煤， 如未经步骤 a) 处 理， 按照一般的溶剂浸取方法提取褐煤蜡， 蜡收率仅为 1. 45%和 1. 78%, 见对比例 2和对比例 3 , 而经步骤 a ) 处理后的蜡收率达 到 2. 28°/。和 3. 51%，见实施例 1和实施例 3。 当在步驟 a )中通入氢 气时， 蜡收率进一步提高， 见实施例 4。 采用烟煤为原料时， 若 未经任何处理直接进行溶剂浸取， 几乎没有检测到符合褐煤蜡特 征的物质（见对比例 4 ) ， 而经过步骤 a )的处理后， 蜡收率可达 到 1. 75% (见实施例 5)。实施例 6是在步骤 a和 b之间加入了用氢 气预处理半焦的步骤， 从结果看， 与仅有相同条件下的步骤 a和 b的实施例 1相比， 蜡收率有了进一步提高。 而其它奈件相同时， 加催化剂显然比不加催化剂时蜡收率要高， 见实施例 1和对比例 1 的对比。 当用两种碳酸盐的复合催化剂时， 蜡收率比单一碳酸 盐作为催化剂时要高， 见实施例 2与实施例 1， 且实施例 2所得 到的褐煤蜡经检测人员目测发现， 其颜色比实施例 1所得的褐煤 蜡更接近纯褐煤蜡的颜色， 证明前者纯度更高。
其中， 蜡收率是指所得到的褐煤蜡占原煤的质量百分比。
表 1
Figure imgf000013_0001

Claims

权 利 要 求
1. 一种提取褐煤蜡的方法， 包括以下步骤：
a)将煤粉在催化剂作用下在亚临界或超临界流体中进行处 理， 得到含有褐煤蜡的半焦；
b)用能够溶解所述褐煤蜡的溶剂将所述褐煤蜡从所述半焦中 浸取出来。
2. 一种提取褐煤蜡的方法， 包括以下步骤：
a)将煤粉在催化剂和氢气的作用下在亚临界或超临界流体中 进行处理， 得到含有褐煤蜡的半焦；
b)用能够溶解所述褐煤蜡的溶剂将所述褐煤蜡从所述半焦中 浸取出来。
3. 权利要求 1或 2的方法， 其中所述超临界是指流体的温度 在其临界温度以上且流体的压力在其临界压力以上； 而所述亚临 界是指流体的温度在其常压沸点以上且在其临界温度以下而流体 的压力为使该流体保持为液态的压力。
4. 根据权利要求 1或 2的方法， 其中步骤 b ) 中所述溶剂为 醇的水溶液、 醇和烃类溶剂的混合物、 酮类溶剂或醚类溶剂。
5. 根据权利要求 4的方法， 其中所述醇选自甲醇、 乙醇、 异 丙醇、 丙二醇或它们的混合物， 所述烃类溶剂选自正己烷、 环己 烷、 溶剂油或它们的混合物。
6. 根据权利要求 1或 2的方法， 其中所述流体选自水、 醇或 二氧化碳。
7. 根据权利要求 1或 2的方法，其中步骤 a)中所述催化剂选 自碱金属或碱土金属氧化物、 碱金属或碱土金属氢氧化物、 或碱 金属或碱土金属盐。
8. 根据权利要求 1或 2的方法， 其中所述煤选自烟煤、 无烟 煤或褐煤。
9. 根据权利要求 1或 2的方法， 其中步骤 a)的反应条件是： 温度为 300- 500 °C ， 压力为 15- 25MPa、 反应时间为 1-30分钟， 催化剂的添加量为所述煤粉的 3-30wt% , 煤与水的质量比为 1: 1-1: 20, 而步骤 b)的浸取条件是： 温度为 65- 200°C , 压力为 0. l-lMPa0
10. 根据权利要求 1或 2的方法， 其中在步骤 a ) 和步驟 b ) 之间增加至少一个在加入水、 氢气、 二氧化碳等物质或其組合的 条件下对半焦进行预处理的步骤。
11. 根据权利要求 1或 2的方法， 其中通过控制步驟 a的催化 剂的种类和 /或组成来控制步骤 b中的被浸取的褐煤蜡的量和 /或 纯度。
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