Composition for biomass oil, and preparation method and use thereof

Abstract

The present invention provides a composition for biomass oil, and a preparation method and use thereof. The composition comprises a biomass and a liquid oil, wherein, based on weight of the biomass, the biomass has a moisture content of 3 wt % to 18 wt %. The biomass is mixed with the liquid oil to obtain a liquid mixture, i.e., the composition for biomass oil. According to the use of the composition for biomass oil in preparation of biomass oil, high-pressure high-temperature hydrolysis is carried out by using water in the biomass, and the polycondensation of coke is avoided under the co-action of hydrogen gas and a catalyst, so that the yield of the coke is lowered, and the yield of the biomass oil is increased.

Claims

1. A method for preparing a composition for biomass oil, the method comprising mixing a biomass with a hydrocracking catalyst and a vulcanizing agent to form a mixture; and then, mixing the mixture with a liquid oil, thereby forming the composition for biomass oil, wherein, based on weight of the biomass, the biomass has a moisture content of 3 wt % to 18 wt %, and wherein, based on a total of 100 parts by weight of the composition for biomass oil, the biomass accounts for 10 parts by weight, the hydrocracking catalyst accounts for 5 parts by weight, and the vulcanizing agent accounts for 0.4 parts by weight.

2. The method according to claim 1, wherein the biomass has a moisture content of 5 wt % to 10 wt %.

Description

DETAILED DESCRIPTION

(1) Example embodiments will now be described more fully with reference to the accompanying drawings.

(2) The technical scheme of the present invention is described below clearly and completely. Apparently, embodiments described are part of embodiments of the present invention, rather than all embodiments. All other embodiments achieved by those having ordinary skill in the art on the premise of not making inventive labor on the basis of the embodiments of the present invention all fall within the protection scope of the present invention.

(3) A composition for biomass oil, provided by the present invention, means a biomass-containing composition and/or mixture for preparing biomass oil, and may be a solution, a slurry or a suspension.

(4) According to the composition for biomass oil, provided by the present invention, the composition comprises a biomass and a liquid oil, wherein, based on weight of the biomass, the biomass has a moisture content of 3 wt % to 18 wt %. Preferably, the biomass has a moisture content of 5 wt % to 10 wt % based on weight of the biomass. The biomass accounts for 10-40 parts by weight, preferably 30-40 parts by weight, based on a total of 100 parts by weight of the composition. Preferably, the composition further comprises a hydrocracking catalyst and a vulcanizing agent. Preferably, based on a total of 100 parts by weight of the composition, the hydrocracking catalyst is added in an amount of 0.1-10 parts by weight, preferably 2-5 parts by weight, and the vulcanizing agent is added in an amount of 0.1-0.5 part by weight.

(5) Active components of conventional hydrocracking catalysts can all be used in the present invention, favorable active components comprise, but are not limited to, one or more selected from hydrogenation-active compounds of transition metals of group VI, group VII and group VIII in the periodic table of elements, such as one or more selected from a group consisting of amorphous iron oxide hydroxide, biomass charcoal loading an active component and amorphous aluminum oxide loading an active component, preferably, aluminum oxide loading molybdenum oxide and nickel oxide. In order to make the hydrocracking catalyst active during reaction, a vulcanizing agent, comprising, but not limited to, sulfur, carbon disulfide and dimethyl disulfide and other common vulcanizing agents in the art, is required to be simultaneously added into the composition for biomass oil.

(6) In the present invention, the biomass mainly means substances such as lignocellulose (lignin for short) such as stalks and trees except for grains and fruits in a farming and forestry production process, leftovers of the agricultural product processing industry, farming and forestry wastes and poultry and livestock faeces and wastes of an animal husbandry production process, comprises stalks of various crops and industrial crops, reeds, trees, tree leaves, algae, vegetable oil, animal oil, swill-cooked dirty oil, animal faeces and so on, and may be feedstocks formed by one or more biomasses. Stalks of crops such as wheat, rice, corn and cotton and high-yield industrial crops such as reeds, pennisetum hydridum and wood sawdust are preferred. Preferably, the biomass is in form of solid particles which have a volume particle size distribution range of 1 to 5,000 microns, preferably 20 to 200 microns.

(7) In the present invention, the liquid oil can be selected from a wide scope and may be at least one selected from a group consisting of vegetable oil, animal oil, coal tar, petroleum and biomass oil.

(8) The present invention further provides a method for preparing the composition for biomass oil, the method comprising a step of mixing a biomass with a liquid oil to obtain a liquid mixture, wherein, based on weight of the biomass, the biomass has a moisture content of 3 wt % to 18 wt %, and preferably, the biomass has a moisture content of 5 wt % to 10 wt %. Preferably, the biomass and the liquid oil are mixed according to a proportion that the biomass accounts for 10-40 parts by weight, preferably 30-40 parts by weight, based on a total of 100 parts by weight of the composition.

(9) A pretreatment procedure is carried out on the biomass prior to mixing the biomass with the liquid oil, and comprises the steps of drying the biomass until the moisture content of the biomass satisfies the above-mentioned requirements, then, crushing the dried biomass to obtain solid biomass particles which have a volume particle size distribution range of 1 to 5,000 microns, preferably 20 to 200 microns, and finally, carrying out dust removal treatment on the solid biomass particles.

(10) The biomass is firstly mixed with the hydrocracking catalyst and the vulcanizing agent prior to mixing the biomass with the liquid oil, wherein, based on a total of 100 parts by weight of the composition, the hydrocracking catalyst is added in an amount of 0.1-10 parts by weight, preferably 2-5 parts by weight, and the vulcanizing agent is added in an amount of 0.1-0.5 part by weight.

(11) The composition for biomass oil, provided by the present invention, is used in preparation of biomass oil. The biomass oil is prepared from the composition for biomass oil by a hydrogenation and hydrolysis process. Specifically, the biomass oil is produced through introducing hydrogen into the composition for biomass oil which is added with the hydrocracking catalyst, and subjecting the composition for biomass oil to hydrolysis under high-temperature and high-pressure conditions. Preferably, the biomass oil is produced through introducing hydrogen until the volume ratio of the hydrogen to the composition for biomass oil reaches (600 to 1,000):1 at a temperature of 250 DEG C. to 550 DEG C., then, carrying out hydrolysis, cracking and hydrogenation reactions for a period of 15 to 90 minutes. The conventional hydrogenation reactors can all be used in the present invention.

(12) According to the biomass oil prepared from the composition for biomass oil, provided by the invention, the yield reaches 60% or more (on dry basis); the combustion performance is good, and the cetane number is greater than 47; the safety is good, and the flashing point is above 47 DEG C.; and the dynamic performance is good, and the calorific value is higher than 41 MJ/kg.

(13) Embodiments for preparation of the composition for biomass oil

Embodiment 1

(14) Wheat straws are dried until the wheat straws have a moisture content of 18 wt %, then, the dried wheat straws are crushed to obtain wheat straw particles which have a volume particle size distribution range of 20 to 200 microns, and finally, dust removal treatment is carried out on the wheat straw particles.

(15) Based on a total of 100 parts by weight of the composition, 5 parts by weight of a hydrocracking catalyst (commercially-available amorphous iron oxide hydroxide) is mixed with the dedusted wheat straw particles, and meanwhile, 0.4 part by weight of sulfur is added as a vulcanizing agent. Then, the obtained mixture and a commercially-available peanut oil are mixed to obtain a mixed slurry according to a proportion that the wheat straw particles account for 35 parts by weight, based on a total of 100 parts by weight of the composition.

Embodiments 2 to 5

(16) The embodiments 2 to 5 adopt processing procedures the same as those in the embodiment 1, and differences are as shown in the following table 1:

(17) TABLE-US-00001 TABLE 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Biomass Name Reeds Pine sawdust Corn stalks Wheat straws Moisture 3 wt % 10 wt % 8 wt % 6 wt % content Liquid oil Lard oil Coal tar Petroleum (wax Biomass oil 1# (anthracene oil oil fraction) or washing oil) Weight proportion of 40 parts by 30 parts by 10 parts by 20 parts by weight biomass in oil product weight weight weight Catalyst 2 parts by 10 parts by 5 parts by 8 parts by weight weight weight weight Vulcanizing agent 0.2 0.5 0.4 0.6

(18) It should be noted that the biomass oil used in the embodiment 5 is biomass oil 4# obtained through subsequent hydrogenation and hydrolysis in the embodiment 4.

Comparative Examples 1 to 2

(19) The comparative examples 1 to 2 adopt processing procedures the same as those in the embodiment 4, and differences are as shown in the following table 2:

(20) TABLE-US-00002 TABLE 2 Comparative example 1 Comparative example 2 Biomass Name Corn stalks Corn stalks Moisture content 2.5 wt % 25 wt %

(21) Embodiments of Use

(22) Biomass oils are prepared from mixed slurries obtained in the embodiments 1 to 5 and the comparative examples 1 to 2 separately by the following method.

(23) The mixed slurry is added into a slurry-bed hydrogenation reactor, and meanwhile, hydrogen is introduced into the hydrogenation reactor until the volume ratio of the hydrogen to the slurry reaches 800:1. Then, a reaction is carried out for a period of 60 minutes under a reaction temperature of 360 DEG C. and a partial pressure of hydrogen of 18 MPa.

(24) The reacted material is subjected to oil-gas separation to obtain a biomass heavy oil, a biomass light oil and a non-condensable gas.

(25) In an embodiment 6, biomass oil is prepared by the following method.

(26) Based on a total of 100 parts by weight of the composition, 5 parts by weight of hydrocracking catalyst (amorphous iron oxide hydroxide) is added into the composition for biomass oil (the composition for biomass oil obtained in the embodiment 4), and meanwhile, 0.4 part by weight of sulfur is added into the composition for biomass oil as a vulcanizing agent, thereby obtaining a feedstock biomass slurry.

(27) The feedstock biomass slurry is added into a slurry-bed hydrolysis and hydrogenation reactor, and meanwhile, hydrogen is introduced into the slurry-bed hydrolysis and hydrogenation reactor until the volume ratio of the hydrogen to the slurry reaches 800:1. Then, a reaction is carried out for a period of 60 minutes under a reaction temperature of 360 DEG C. and a partial pressure of the hydrogen of 18 MPa.

(28) The reacted material is subjected to gas-oil separation to obtain a biomass heavy oil, a biomass light oil and a non-condensable gas.

(29) The biomass oils obtained in the embodiments 1 to 5, the comparative examples 1 to 2 and the embodiment 6 are separately marked as 1#, 2#, 3#, 4#, 5#, 6#, 7# and 8#. Reaction results of all samples are as shown in the following table 3.

(30) TABLE-US-00003 TABLE 3 1# 2# 3# 4# 5# 6# 7# 8# Conversion 95 93 96 98 97 87 91 94 ratio of biomass, wt % Yield of 66 62 67 72 69 43 47 61 biomass oil (on dry basis of biomass), wt % Coke yield, 0.5 0.9 0.3 0.1 0.2 7 9 1.0 wt % Oxygen 4.0 3.8 3.5 2.8 3.1 7.0 8.2 4.5 content of biomass oil, wt %

(31) In the above table, a calculation formula for the conversion ratio of biomass oil is as follows: gas+biomass light oil+biomass heavy oil/biomass (dry basis).

(32) A calculation formula for the yield of biomass oil is as follows: biomass light oil+biomass heavy oil/biomass (dry basis).

(33) A calculation formula for coke yield is as follows: solid-state residue/biomass (dry basis).

(34) The oxygen content of biomass oil is measured by gas chromatography-mass spectrography.

(35) Apparently, the above-mentioned embodiments are only illustrated for distinct description, but are not intended to limit embodiments. For those having ordinary skill in the art, changes or variations of other different forms can also be made on the basis of the above-mentioned description. Herein, all embodiments are not required to and cannot be exhaustive. Readily apparent changes or variations evolved therefrom still fall within the protection scope of the present invention.

(36) The foregoing description of the embodiments has been provided for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosure. Individual elements or features of a particular embodiment are generally not limited to that particular embodiment, but, where applicable, are interchangeable and can be used in a selected embodiment, even if not specifically shown or described. The same may also be varied in many ways. Such variations are not to be regarded as a departure from the disclosure, and all such modifications are intended to be included within the scope of the disclosure.