WO2012129783A1

WO2012129783A1 - Process for producing liquid hydrocarbon fuel by coal hydrolysis

Info

Publication number: WO2012129783A1
Application number: PCT/CN2011/072281
Authority: WO
Inventors: 朱作霖; 孙萌; 苏春高
Original assignee: 淮北中润生物能源技术开发有限公司; 美国升阳制药公司
Priority date: 2011-03-30
Filing date: 2011-03-30
Publication date: 2012-10-04

Abstract

A process for producing liquid hydrocarbon fuel from coal is provided, wherein cellulose is used to assist the coal hydrolysis, and the hydrolyzed product is subjected to hydrogenation reaction to obtain the liquid hydrocarbon fuel.

Description

Process for preparing liquid hydrocarbon fuel by hydrolysis of coal

Technical field

The invention relates to a novel production process for preparing liquid hydrocarbon fuel from coal as a raw material, in particular, to first catalyze the hydrolysis of coal into small molecular organic matter, and then hydrogenate it under conditions which are milder than current coal liquefaction conditions. Liquid hydrocarbon fuel process and production process. Background technique

The reserves of coal in the earth are much higher than the reserves of oil. At the beginning of this century, petroleum energy has entered the peak of its supply. Under the current technological conditions of human society, liquid hydrocarbon fuels are irreplaceable for a long period of time. Humans are trying different methods of preparing liquid hydrocarbon fuels from coal. The known methods require relatively high defects and require high coal quality and industrialization. For example, the direct liquefaction reaction conditions are quite harsh, the temperature is close to 500 ° C, the pressure exceeds 150 kg of hydrogenation reaction system; the coal gasification indirect method produces liquid hydrocarbon fuel, the gasification temperature exceeds iooo ° c, and the requirements for coal quality It is very high, and because of the high content of sulfur, nitrogen, heavy metals, etc. in the coal, the reaction process control and reaction equipment needs to deal with sulfur, nitrogen, heavy metals, etc., and the process is complicated and requires high equipment.

In order to be able to produce hydrocarbon liquid fuel as raw material as soon as possible, it is necessary to develop mild reaction conditions, drastically reduce production costs, and have low requirements on coal quality. The sulfur, nitrogen and heavy metals in coal have little or no effect on the hydrogenation process. The technology and production process of coal-based hydrocarbon liquid fuel without impact. In particular, lignite (Ligni te), because of its high oxygen content and ash content, but has a large reserve, for example, accounting for 13% of China's coal reserves, it is of great significance to convert it into a hydrocarbon liquid fuel.

Therefore, there is an urgent need in the art for a mildly prepared method for preparing liquid hydrocarbon fuels from coal as a raw material; more urgently, there is a need for a method for obtaining liquid hydrocarbon fuels from coals having low coal quality requirements. Summary of the invention

The object of the present invention is to provide a new production process for preparing liquid hydrocarbon fuel from coal. The core of this new production process is coal hydrolysis, which then hydrolyzes the hydrolyzed product to alkane, a liquid hydrocarbon fuel. The temperature and pressure of the hydrolysis reaction and the hydrogenation reaction are greatly reduced with respect to direct liquefaction or indirect liquefaction of coal, and sulfur, nitrogen, heavy metals, etc. in the coal have little or no effect on the hydrogenation process, effectively reducing The production cost of preparing liquid hydrocarbon fuel from coal. The method for preparing liquid hydrocarbon fuel by using coal as raw material for the first time realizes catalytic hydrolysis of coal for the first time, which comprises the following steps: First, coal is hydrolyzed into small molecules in the presence of cellulose. Organic compound; In the second step, the aromatic compound obtained by hydrolysis is subjected to hydrogenation saturation conversion to an alkane compound, that is, a liquid hydrocarbon fuel. A first aspect of the invention provides a method of preparing a hydrocarbon liquid fuel using coal hydrolysis, comprising the steps of:

a first step of providing a mixture of coal and optionally cellulose; wherein the proportion of the coal is not lower than

50%, based on the total weight of the mixture;

In the second step, the mixture obtained in the first step is subjected to a hydrolysis reaction to obtain a hydrolyzed product in which the coal is depolymerized and the sulfur and nitrogen in the coal are greatly reduced;

In the third step, the hydrolyzed product is converted into a high calorific value hydrocarbon liquid fuel by a hydrogenation reaction. In a specific embodiment of the present invention, in the second step, the sulfur nitrogen and ash are substantially reduced: the hydrolyzed product is reduced by not less than 85% relative to the sulfur content of the coal in the first step, and the nitrogen content is The reduction is not less than 95%; the reduction of ash content is not less than 90%, calculated based on the weight of coal in the first step. In a specific embodiment of the present invention, in the second step, the temperature of the hydrolysis reaction is lower than 250 ° C, and the pressure is lower than 4. 6 MPa; preferably, the reaction temperature of the hydrolysis reaction is 180 to 250 ° C. In a specific embodiment of the present invention, in the second step, the hydrolysis reaction catalyst for coal hydrolysis is a substance represented by Formula 1 and Formula 2, or a substance converted into Formula 1 or Formula 2 in water.

Μ I——S Η or

Formula two

In the formula,

"M" means metal, carbon, or silicon;

"S" indicates a hetero atom; "L" represents one or more ligands;

"H" means hydrogen.

01至100百分比。 The catalyst is used in an amount of from 0.1 to 100% by weight of the coal.

In a preferred embodiment, the hetero atom means "oxygen 0", "sulfur S", or "nitrogen N".

In a preferred embodiment, the metal is selected from the group consisting of transition metals.

In a preferred embodiment, the catalyst is a material which is water-soluble and which can be converted into a "form one" or "form two" structure upon entering the aqueous phase.

In a preferred embodiment: the material which can be converted into a "Formula 1" or "Formula 2" structure is a water-soluble metal inorganic salt, a metal organic acid salt or a combination thereof. In a specific embodiment of the invention, the hydrolysis of the coal is carried out in the presence of cellulose, and the ratio between cellulose and coal is between 1:100 and 1:1.

In a preferred embodiment, the ratio between cellulose and coal is 1: 5 to 1: 1. In a specific embodiment of the invention, the cellulose is cellulose present in pure cellulose, or a cellulose-containing material.

Preferably, the cellulose-containing substance (impure cellulose) is selected, for example, from cellulosic biomass; the "cellulose present in the cellulose-containing substance" means cellulose biomass and lignin, etc. The cellulose present at the same time. In one embodiment of the invention, when cellulosic biomass is employed, the total amount of cellulose and hemicellulose therein is at least one third of the weight of the coal.

As used herein, "hemicellulose" refers to a heterosaccharide polymer in a plant. In a particular embodiment of the invention, the hydrogenation of the hydrolysate is carried out by catalytic hydrogenation or by catalytic transfer hydrogenation. In a specific embodiment of the present invention, in the catalytic transfer hydrogenation reaction, the source of hydrogen is methanol, and the hydrogenation catalyst is porous copper magnesium aluminum metal oxide (Cu-PMO). In a specific embodiment of the present invention, the high calorific value hydrocarbon liquid fuel is selected from the group consisting of oxygen Or a saturated hydrocarbon that does not contain oxygen. BEST MODE FOR CARRYING OUT THE INVENTION

The present invention relates to a process for producing a liquid hydrocarbon fuel by using coal in the presence of cellulose, which may be pure cellulose or other substances containing cellulose such as plants (cellulosic biomass ig _Noce llul _OSe ). Because although the ability of cellulose biomass to assist coal hydrolysis is less than that of pure cellulose, cellulosic biomass is preferred as cellulose because it does not require purification of cellulose, reduces purification costs, and has low production costs for using cellulosic biomass. source.

The invention has been subjected to a large number of experiments to obtain a production process for preparing liquid hydrocarbon fuel by using coal as a raw material, and comparing the known coal direct liquefaction or indirect liquefaction production process, the reaction condition is quite mild, and the whole production process route is The temperature does not exceed 250 ° C, the pressure does not exceed 50 kg, compared to direct liquefaction or indirect liquefaction of coal, the temperature drops by more than 50%, the pressure drops by more than two-thirds, resulting in a significant drop in production costs.

The new production process disclosed by the present invention, because of the use of hydrolysis, does not require drying treatment of coal, further saves energy consumption, and can use lignite having the worst coal quality as a raw material. The present invention has been completed on this basis.

The prior art methods for preparing liquid hydrocarbon fuels for raw materials are carried out under very demanding conditions, and the production cost and energy consumption are relatively high, and it is difficult to promote the application. The inventors have found that the oxygen atoms in the organic molecules of the polymer in coal are basically in the form of aromatic ether bonds, similar to the lignin structure. The cellulosic biomass synchronous hydrolysis catalyst system invented by us can effectively catalyze the hydrolysis of organic polymer molecules containing ether bonds in coal, thereby obtaining small molecular organic products.

The inventors have also discovered that the development of coal hydrolysis to produce hydrocarbon liquid fuels has great advantages. First of all, the catalytic hydrogenation conditions of small molecule organic matter are quite mild, and because of the small molecular size and high solubility, it can be effectively combined with the catalyst, and the reaction speed is fast. Insoluble catalyst (solid phase catalysis) can be used, and the continuous fixed bed catalytic technology is mature. Easy to operate. However, the polymer has large molecular weight, poor solubility, and difficult combination with a catalyst, and the reaction conditions are severe. This is the main reason for the high cost of direct liquefaction and indirect liquefaction of coal.

The advantage of coal hydrolyzing to prepare liquid hydrocarbon fuels comes from hydrolysis, because hydrolysis has many advantages, including relatively mild reaction conditions. The hydrolysis reaction uses water molecules to open the bonds containing heteroatoms in the high polymer. Therefore, the hydrolysis can convert many sulfur and nitrogen in the coal into water-soluble sulfur and nitrogen to achieve the removal of sulfur and nitrogen, so that the catalyst life of the hydrogenation reaction is greatly increased. Extends, and greatly reduces the emission of sulfur and nitrogen into the atmosphere during the production of hydrocarbon liquid fuel. At the same time, because the ash in coal is difficult to hydrolyze, hydrolyze Most of the ash can be removed, thereby greatly increasing the efficiency of the hydrogenation reaction. Various aspects of the invention are detailed below:

Unless otherwise specified, various starting materials of the present invention can be obtained commercially, or can be prepared according to conventional methods in the art. Unless otherwise defined or indicated, all of the professional and scientific terms used herein have the same meaning as those skilled in the art. Furthermore, any methods and materials similar or equivalent to those described may be employed in the methods of the invention. Cellulose and coal

The coal hydrolysis disclosed in the present invention is carried out in the presence of cellulose, and the cellulose may be pure cellulose, such as a cellulose product obtained by removing lignin and hemicellulose by various methods, or may be recovered. The white paper can also be recycled cotton. The cellulose in the process of coal hydrolysis may also be untreated cellulosic biomass. The cellulose biomass (1 ignocellulose) referred to in the present invention meets an important requirement: whether it is a herb or a woody plant, The cellulose content is higher than the lignin content.

The coal according to the present invention is not particularly limited, and as long as the object of the present invention is not limited, it is preferable to use the lignite having the lowest cost.

In the hydrolysis mixture, the ratio between the cellulosic biomass and the coal may be between 1:100 and 1:1, preferably the weight of the cellulose is close to the weight of the coal, or, if the cellulosic biomass is used directly, the cellulosic biomass The cellulose and hemicellulose are present in an amount of at least one third of the weight of the coal. Catalyst

In one embodiment of the invention, the agent has the following structure:

Μ I——S Η or

Formula two

In the formula,

"M" means metal, carbon, silicon, etc.;

"S" indicates a hetero atom such as "oxygen 0", S", "nitrogen N", etc.;

"L" indicates a ligand, which may be one or more;

"H" means hydrogen.

Since the compound of formula 1 and the compound of formula 2 can be converted into each other, we understand that the catalyst The agent can be:

a compound having a structure of its own;

a compound having a structure of the formula II;

Also included are water-soluble, substances that can be converted into "structure-in-structure" when entering the aqueous phase, and also include water-soluble, and the metal that enters the aqueous phase can be converted into a "structured structure". The metal is not specifically limited, as long as It does not affect the conversion of the acetal bond and the ether bond of the present invention. For example, including but not limited to copper, palladium, platinum, nickel, mercury, and the like elements of the above metals.

For example, metal hydrochlorides, such as copper chloride, palladium chloride, platinum chloride, nickel chloride, and the like, metal organic acid salts such as mercuric acetate, copper acetate, and the like:

More specifically, for example, a metal hydrochloride salt, specifically, for example, copper chloride, palladium chloride, platinum chloride, nickel chloride or the like. It may also be a metal organic acid salt such as mercury acetate, copper acetate or the like. The organic acid salt may also be another water-soluble organic acid salt, but it must be water-soluble and can be converted to L-M-0H or L-M = 0 when dissolved in water. If the material is not water soluble or cannot be converted to formula 1 or formula 2, it is not a catalyst.

The inventors of the present invention have provided a novel catalytic system, which is a catalyst in a reduced state, and an oxidation state in the second embodiment, which can be converted into each other. That is to say, we can understand that the formula 1 is added to the reaction, and it will be converted into the substance of the formula II in the reaction. Otherwise, the formula 2 will be converted into the formula 1.

The amount of the catalyst may be a catalytic amount, generally 0.1 to 100% by weight of the coal, and the amount of the catalyst not in this range may also catalyze the reaction, but the amount of the catalyst is lower than this range. Slow, not preferred; the amount of catalyst above this interval is too high and not preferred. Hydrogenation reaction

For the product obtained by hydrolysis of coal, all hydrogenation reactions, preferably catalytic hydrogenation and catalytic hydrogen transfer, can be used.

The catalytic hydrogenation and transfer hydrogenation are known to those skilled in the art. The following examples are given to better illustrate the invention and are not intended to disclose the invention. The content is limited to the following embodiments. The catalysts disclosed herein include all materials that conform to the structures described above.

The coal used in the examples was lignite (the content generally used is a weight content of Wt%), the ash content was 23%, the moisture content was 31%, and the heat of combustion was 21 MJ/kg. After the ash and water are deducted, the elemental composition is 69.5%, the hydrogen content is 5.4%, the sulfur content is 1. 1%, the oxygen content is 24%, and the nitrogen content is 0.81%.

, pulverized into particles of about 1 mm, and the water content after pulverization is 18%. The cellulose source used in the examples is wheat straw (pulverized to about 1 mm, cellulose 41%, hemicellulose 20%, lignin 21%), recycled waste paper (about 1 mm particles, cellulose content) 89%).

Example 1 : A catalyst which can be converted into a "Formula 1" structure in water: tetra-p-phenylsulfonate iron sodium (corresponding to

60 g of crushed lignite and 40 g of pulverized dried wheat straw, 1 g of sodium tetra-p-benzene sulfonate, 800 ml of a 4.5% aqueous sodium hydroxide solution, all added to a 1000 ml stainless steel high-pressure reactor. The reaction system was sealed, heated to a temperature of 250 ° C, held for 100 minutes, and then cooled back to room temperature. No change was observed in the pressure before and after the reaction (no gasification reaction occurred). After the reaction mixture product was taken out, the reactor was washed twice with a small amount of pure water, and no blot of the carbonization reaction was found in the reaction vessel. The reaction mixture and the washing liquid were combined, filtered, and the filter residue was washed twice with a small amount of pure water and dried in a vacuum. The weight was 21 g (ash content 68%), and the hydrolysis rate was 79% (after deducting the inherent ash, the hydrolysis rate was 93%). 5克。 After the filtration of the aqueous solution, the pH was adjusted to 3. 5-4, using MTBE extraction 3 times (3X200 ml), the black liquid obtained after the recovery of MTBE, the weight of 58.8 grams. Elemental analysis showed that the empirical formula of the black liquid was C ₁₅₉ H ₁₆₅ O ₄₈ (C content 67.18%, H content 5.83%, 0 content 26.98%), and 7 water molecules were added to the lignite empirical molecule. At the same time, the sulfur content in the black liquid is 53ppm, contrast brown The coal desulfurization rate was 95%; no nitrogen was detected in the black liquid, the ash content was 2.1%, and the lignite deashing rate was 91%. The results show that hydrolysis is a good means of desulfurization and deashing. Example 2: Catalytic hydrolysis of LM=0 catalyst (catalyst: sodium perrhenate NaRe0 ₄ , corresponding catalyst formula, M=Re, S=0)

60 grams of crushed lignite and 40 grams of pulverized dried wheat straw, 1 gram of sodium perrhenate, 800 ml of a 4.5% aqueous solution of sodium hydroxide, all added to a 1000 ml stainless steel high pressure reactor, sealing the reaction system, Heat to 250 ° C, keep warm for 100 minutes and then cool back to room temperature. No change was observed in the pressure before and after the reaction (no gasification reaction occurred). After the reaction mixture product was taken out, the reactor was washed twice with a small amount of pure water, and no blot of the carbonization reaction was found in the reaction vessel. The reaction mixture and the washing liquid were combined, filtered, and the filter residue was washed twice with a small amount of pure water and dried in a vacuum. The weight is 19 g (ash content 74%), and the hydrolysis rate is 81% (after deducting the inherent ash, the hydrolysis rate is 95%). The aqueous solution obtained by filtration, adjusted to pH=3. 5-4, extracted with 3 times of MTBE (3×200 ml), evaporated to give a black liquid obtained after recovery of MTBE, weight: 60. 1 g, Hydrocarbon element analysis and Example 1 basically the same. Elemental analysis showed that the sulfur content in the black liquid was 55 ppm, and the desulfurization rate of the lignite was 95%; the ash content was 2.3%, and the lignite deashing rate was 91%. Example 3: Catalyst: Mercury trifluoroacetate Hg (0C0CF ₃ ) ₂ (can be converted to LM-0H type catalyst in water, corresponding to the catalyst formula M=Hg, S=0)

60 g of crushed lignite and 40 g of pulverized dried wheat straw, 1 g of mercury trifluoroacetate, 800 ml

4. A 5% aqueous solution of sodium hydroxide was added to a 1000 ml stainless steel high pressure reactor. The reaction system was sealed, heated to a temperature of 250 ° C, held for 100 minutes, and then cooled back to room temperature. No change was observed in the pressure before and after the reaction (no gasification reaction occurred). After the reaction mixture product was taken out, the reactor was washed twice with a small amount of pure water, and no blot of the carbonization reaction was found in the reaction vessel. The reaction mixture and the washing liquid were combined, filtered, and the filter residue was washed twice with a small amount of pure water and dried in a vacuum. The weight was 26 g (54% ash content) and the hydrolysis rate was 74% (after deducting the inherent ash, the hydrolysis rate was 86%). The liquefied solution of the hydrocarbons, and the weight of the black liquid obtained by the recovery of the MTBE, the weight of 51.3 g, the analysis of the hydrocarbon element and the example 1 basically the same. Elemental analysis showed that the sulfur content in the black liquid was 48 ppm, and the desulfurization rate of the lignite was 96%; the ash content was 2.5%, and the degumming rate of the lignite was 90%. Example 4: Porous metal oxide (Ni-PMO) catalyst (capable of conversion to LM-0H catalyst in water, corresponding to catalyst in the formula M = Ni, S = 0)

The synthesis of the porous metal oxide (Ni-PMO) is carried out by the literature method (US 7, 442, 323 B2), and the metal ratio is Mg : Al : Ni = 2. 3 : 1 : 0.2.

60 g of crushed lignite and 40 g of pulverized dried wheat straw, 100 mg of Ni-PM0, 800 ml of a 4.5% aqueous sodium hydroxide solution, all added to a 1000 ml stainless steel high pressure reactor, sealed reaction system, heated After cooling to 250 ° C for 100 minutes, cool to room temperature. No change was observed in the pressure before and after the reaction (no gasification reaction occurred). After the reaction mixture product was taken out, the reactor was washed twice with a small amount of pure water, and no blot of the carbonization reaction was found in the reaction vessel. The reaction mixture and the washing liquid were combined, filtered, and the filter residue was washed twice with a small amount of pure water and dried in a vacuum. The weight was 29 g (ash content 46%) and the hydrolysis rate was 71% (after deducting the inherent ash, the hydrolysis rate was 83%). The liquefied aqueous solution, the weight of the black liquid obtained by the recovery of the MTBE, the weight of 46.3 g, the hydrocarbon element analysis and the example 1 basically the same. Elemental analysis showed that the sulfur content in the black liquid was 51 ppm, and the desulfurization rate of the lignite was 95%; the ash content was 1.8%, and the deashing rate of the lignite was 92%. Example 5: polyoxometallate (Na ₃ PW ₁₂ 0 ₄ ) catalyst (LM = 0, corresponding to the catalyst formula M = W, S = 0)

60 g of crushed lignite and 40 g of pulverized dried wheat straw, 300 mg of Ni-PM0, 800 ml of 4.5% aqueous sodium hydroxide solution, all added to a 1000 ml stainless steel high pressure reactor, sealed reaction system, heated After cooling to 250 ° C for 100 minutes, cool to room temperature. No change was observed in the pressure before and after the reaction (no gasification reaction occurred). After the reaction mixture product was taken out, the reactor was washed twice with a small amount of pure water, and no blot of the carbonization reaction was found in the reaction vessel. The reaction mixture and the washing liquid were combined, filtered, and the filter residue was washed twice with a small amount of pure water and dried in a vacuum. The weight was 23 g (yield 58%) and the hydrolysis rate was 77% (after deducting the inherent ash, the hydrolysis rate was 90%). The liquefied aqueous solution, the weight of the black liquid obtained by the recovery of the MTBE, the weight of 53.3 g, the analysis of the hydrocarbon element and the example 1 basically the same. Elemental analysis showed that the sulfur content in the black liquid was 51 ppm, compared with 95% for the desulfurization rate of lignite; the ash content was 2.5%, and the deashing rate of lignite was 90%. Example 6: LM-0H type catalyst (corresponding to the catalyst formula M = Mn, S = 0) As shown below.

The solvent is a 50% aqueous methanol solution (volume ratio), and the solution is dissolved in 4.9 g of manganese acetate tetrahydrate (2 mmol), and 7.68 g of the ligand (2 mmol), and then 30% is added dropwise. An aqueous solution of potassium hydroxide (4 mmol for converting the phenolic hydroxyl group of the ligand to a potassium salt). After refluxing for 50 minutes, the yellow-brown solid product was filtered, and the product was washed several times with 50% aqueous methanol and dried in vacuo. Elemental analysis: manganese (Mn) 12. 18%, carbon (C) 52.63%, nitrogen (N) 6. 38% Molecular formula L- Mn- OH (MnC _2Q H ₁₉ N ₂ 0 ₇ ) Theoretical content: Manganese ( Mn) 12. 09%, carbon (C) 52. 87%, nitrogen (N) 6. 17%. Infrared (IR, cm-spectrum: 421 (w, vMn-0), 878 (m, yCH), 991 (m, 6CH), 1021 (w, vC-OC), 1085 (m, 60H), 1 152 ( s, vC- 0), 1 191 (w, vC-0-C) , 1273 (vs , vC-N) , 1391 (m, 6CH ₃ ) , 1451 (m, 6CH ₂ ) , 1600 (vs , vC= C), 1624 (vs, vC=N), 1679 (m, vC=0).

60 g of crushed lignite and 40 g of pulverized dried wheat straw, 100 mg of catalyst, 800 ml of 4.5% aqueous sodium hydroxide solution, all added to a 1000 ml stainless steel high pressure reactor, sealed reaction system, heated to 250 ° C temperature, keep warm for 100 minutes and then cool back to room temperature. No change was observed in the pressure before and after the reaction (no gasification reaction occurred). After the reaction mixture product was taken out, the reactor was washed twice with a small amount of pure water, and no blot of the carbonization reaction was found in the reaction vessel. The reaction mixture and the washing liquid were combined, filtered, and the filter residue was washed twice with a small amount of pure water and dried in a vacuum. The weight was 31 g (44% ash content) and the hydrolysis rate was 69% (after deducting the inherent ash, the hydrolysis rate was 83%). The liquefied aqueous solution, the weight of the black liquid obtained by the recovery of the MTBE, the weight of 40.8 g, the hydrocarbon element analysis and the example 1 basically the same. Elemental analysis showed that the sulfur content in the black liquid was 55 ppm, the desulfurization rate of the lignite was 94%, the ash content was 1.5%, and the lignite deashing rate was 92%. Example 7: L-M=0 catalyst (2,3-dichloro-5,6-dicyanobenzoquinone, DDQ, corresponding catalyst in the formula M=C, S=0)

60 g of crushed lignite and 40 g of pulverized dried wheat straw, 200 mg of catalyst, 800 ml of 4.5% aqueous sodium hydroxide solution, all added to a 1000 ml stainless steel high pressure reactor, sealed reaction system, heated to 250 ° C temperature, keep warm for 100 minutes and then cool back to room temperature. Pressure before and after reaction No changes were observed in the force (no gasification reaction occurred). After the reaction mixture product was taken out, the reactor was washed twice with a small amount of pure water, and no blot of the carbonization reaction was found in the reaction vessel. The reaction mixture and the washing liquid were combined, filtered, and the filter residue was washed twice with a small amount of pure water and dried in a vacuum. The weight is 25 g (ash content 55%) and the hydrolysis rate is 75% (after deducting the inherent ash, the hydrolysis rate is 89%). The liquefied aqueous solution, the weight of the black liquid obtained by the recovery of the MTBE, the weight of 46.3 g, the hydrocarbon element analysis and the example 1 basically the same. Elemental analysis showed that the sulfur content in the black liquid was 49 ppm, and the desulfurization rate of the lignite was 95%; the ash content was 1.7%, and the deashing rate of the lignite was 92%. Example 8: LM-0H type catalyst (catalyst: ruthenium, corresponding catalyst formula M=C, S=0)

60 g of crushed lignite and 40 g of pulverized dried wheat straw, 500 mg of catalyst, 800 ml of 4.5% aqueous sodium hydroxide solution, all added to a 1000 ml stainless steel high pressure reactor, sealed reaction system, heated to 250 ° C temperature, keep warm for 100 minutes and then cool back to room temperature. No change was observed in the pressure before and after the reaction (no gasification reaction occurred). After the reaction mixture product was taken out, the reactor was washed twice with a small amount of pure water, and no blot of the carbonization reaction was found in the reaction vessel. The reaction mixture and the washing liquid were combined, filtered, and the filter residue was washed twice with a small amount of pure water and dried in a vacuum. The weight was 27 g (ash content 51%) and the hydrolysis rate was 73% (after deducting the inherent ash, the hydrolysis rate was 87%). 5克, Hydrocarbon element analysis and Example 1 The aqueous solution obtained by filtration was adjusted to pH = 3. 5-4, extracted with 3 times (3×200 ml) using MTBE, and the black liquid obtained after the recovery of MTBE was distilled off, weight 42.7 g, hydrocarbon element analysis and example 1. basically the same. Elemental analysis showed that the sulfur content in the black liquid was 48 ppm, the desulfurization rate of the lignite was 95%, the ash content was 1.6%, and the deashing rate of the lignite was 92%. Example 9: ethylenediamine is used as a catalyst (corresponding to the catalyst formula M=C,

S=N)

60 grams of crushed lignite and 40 grams of pulverized dried wheat straw, 1 gram of ethylene diamine, 800 ml of 4.5% aqueous sodium hydroxide solution, all added to a 1000 ml stainless steel high pressure reactor, sealing the reaction system, heating After cooling to 250 ° C for 100 minutes, cool to room temperature. No change was observed in the pressure before and after the reaction (no gasification reaction occurred). After the reaction mixture product was taken out, the reactor was washed twice with a small amount of pure water. No imprinting of the carbonization reaction was found in the reaction vessel. The reaction mixture and the washing liquid were combined, filtered, and the filter residue was washed twice with a small amount of pure water and dried in a vacuum. The weight was 33 g (the ash content was 41%), and the hydrolysis rate was 67% (excluding the inherent ash, the hydrolysis rate was 81%). Water soluble after filtration The liquid and the hydrochloric acid were adjusted to pH=3. 5-4, and extracted with 3 times (3×200 ml) by MTBE, and the black liquid obtained by recovering MTBE was distilled off, and the weight was 38.8 g. The hydrocarbon element analysis was substantially the same as in Example 1. Elemental analysis showed that the sulfur content in the black liquid was 58 ppm, and the desulfurization rate of the lignite was 94%; the ash content was 2.6%, and the degumming rate of the lignite was 90%. Example 10: 2,6-dithionaphthalene as a catalyst (corresponding to the catalyst formula M=C, S=S)

2,6-naphthylthiol was synthesized using literature methods (US 5,338,886).

60 g of crushed lignite and 40 g of pulverized dried wheat straw, 500 mg of 2,6-naphthyl mercaptan, 800 ml of 4.5% aqueous sodium hydroxide solution, all added to a 1000 ml stainless steel high pressure reactor, sealed The reaction system was heated to a temperature of 250 ° C, held for 100 minutes, and then cooled back to room temperature. No change was observed in the pressure before and after the reaction (no gasification reaction occurred). After the reaction mixture product was taken out, the reactor was washed twice with a small amount of pure water, and no blot of the carbonization reaction was found in the reaction vessel. The reaction mixture and the washing liquid were combined, filtered, and the filter residue was washed twice with a small amount of pure water and dried in a vacuum. The weight was 38 g (ash content: 35%), and the hydrolysis rate was 52% (excluding the inherent ash, the hydrolysis rate was 75%). 4克, Hydrocarbon element analysis and Example 1 The aqueous solution obtained by filtration was adjusted to pH=3. 5-4, extracted with 3 times of MTBE (3×200 ml), and the black liquid obtained by recovering MTBE was distilled off, and the weight was 31.4 g. basically the same. Elemental analysis showed that the sulfur content in the black liquid was 162 ppm, compared with 85% in the desulfurization rate of lignite; the ash content was 2.5%, and the deashing rate of lignite was 90%. Example 11: Effect of different cellulosic biomass, the catalyst was L-Mn-0H (MnC _2Q H ₁₉ N ₂ O ₇ ) 70 g of pulverized brown coal and 30 g of pulverized recycled white paper, 100 mg of MnC ₂ . H ₁₉ N ₂ 0 ₇ , 800 ml of a 4.5% aqueous sodium hydroxide solution, all added to a 1000 ml stainless steel high pressure reactor, sealed the reaction system, heated to 250 ° C temperature, kept for 100 minutes and then cooled back to room temperature . No change was observed in the pressure before and after the reaction (no gasification reaction occurred). After the reaction mixture product was taken out, the reactor was washed twice with a small amount of pure water, and no blot of the carbonization reaction was found in the reaction vessel. The reaction mixture and the washing liquid were combined, filtered, and the filter residue was washed twice with a small amount of pure water and dried in a vacuum. The weight was 18 g (88% ash content) and the hydrolysis rate was 82% (after deducting the inherent ash, the hydrolysis rate was 98%). 4克, Hydrocarbon element analysis and Example 1 The aqueous solution obtained by filtration was adjusted to pH=3. 5-4, extracted with 3 times (3×200 ml) using MTBE, and the black liquid obtained after the recovery of MTBE was distilled off, and the weight was 53.4 g. basically the same. Elemental analysis showed that the sulfur content in the black liquid was 42 ppm, compared with 96% in the desulfurization rate of lignite; 1. 5%, compared with 92% for lignite. Example 12: No catalyst control

60 grams of crushed brown coal and 40 grams of pulverized dried wheat straw, 800 ml of 4.5% aqueous sodium hydroxide solution, all added to a 1000 ml stainless steel high pressure reactor, sealed reaction system, heated to 250 ° C temperature, heat preservation After 100 minutes, it was cooled back to room temperature. No change was observed in the pressure before and after the reaction (no gasification reaction occurred). After the reaction mixture product was taken out, the reactor was washed twice with a small amount of pure water, and no blot of the carbonization reaction was found in the reaction vessel. The reaction mixture and the washing liquid were combined, filtered, and the filter residue was washed twice with a small amount of pure water, and dried under vacuum, and the residue was analyzed by filtration. The weight is 63 grams (24% ash content), the hydrolysis rate is 37%, the analysis shows that the solids do not contain cellulose and hemicellulose, the weight loss is mainly caused by cellulose and hemicellulose in wheat straw, and coal. A small amount of substance. The aqueous solution obtained after filtration was adjusted to pH = 3. 5-4 by hydrochloric acid, and extracted with 3 times of MTBE (3×200 ml), and the black liquid obtained by recovering MTBE was distilled off, and the weight was 3. 4 g. There is no catalyst and there is very little reaction.

Example 13: Hydrogenation of a hydrolyzed black liquid product, 5% palladium on carbon (Pd/C) catalyst

The continuous tubular reactor had a catalyst fill volume of 10 ml and was filled with a 5% palladium on carbon catalyst. The black liquid obtained by the hydrolysis was dissolved in methanol to prepare a 10% solution. The reaction temperature was 180 ° C, the hydrogen pressure was 6 MPa, the inlet speed was 50 standard cc/min, the feed rate was 0.1 ml/min, and the color of the reaction product was light brownish yellow, and a total of 500 ml of liquid was collected. After carefully distilling off the methanol solvent, a brown liquid product was obtained. The elemental analysis showed that the obtained product had an empirical formula of C ₁₅₉ H ₃₁₁ O ₃₉ (C content: 67. 1%, H content 10.98%, 0 content 21. 92%). ), the heat of combustion is 39MJ/kg.

Example 14: Hydrogenation of a hydrolyzed black liquid product, hydrogen transfer reaction

The synthesis of the green porous copper-magnesium-aluminum metal oxide (Cu-PMO) is carried out by the literature method (US 7, 442, 323B2), and the metal ratio is Mg : Al : Cu = 3. 3 : 1 : 0.3.

The catalyst of the continuous tubular reactor was filled in a volume of 10 ml, and mixed with porous copper-magnesium-aluminum metal oxide (Cu-PMO) 30% and 70% activated carbon as a catalyst. The black liquid obtained by the hydrolysis was dissolved in methanol to prepare a 10% solution. The reaction temperature was 210 ° C, nitrogen was used to maintain a pressure of 9 MPa, the inlet speed was 5 standard cc/min, the feed rate was 0.1 ml/min, and the color of the reaction product was light brownish yellow, and a total of 500 ml of liquid was collected. The 5%, the content of the product is C ₁₅₉ H ₂₉₉ O ₄₅ (C content 65. 2%, H content 10.3%, 0 content 24.5%). ), the heat of combustion is 36MJ/kg.

Claims

Rights request

A method for preparing a hydrocarbon liquid fuel by hydrolyzing coal, comprising the steps of:

50%, based on the total weight of the mixture;

In the third step, the hydrolyzed product is converted into a high calorific value hydrocarbon liquid fuel by a hydrogenation reaction.

2. The method according to claim 1, wherein in the second step, the sulfur nitrogen and the ash are substantially reduced, that is, the hydrolyzate is not lower than the sulfur content of the coal in the first step. 85%, the reduction of nitrogen content is not less than 95%; the reduction of ash content is not less than 90%, calculated by the weight content of coal in the first step.

3. The method according to claim 1, wherein in the second step, the temperature of the hydrolysis reaction is lower than 250 ° C, and the pressure is lower than

4. 6MPa; Preferably, the hydrolysis reaction has a reaction temperature of 180 to 250. C o 4. The method of claim 1 wherein:

In the second step, the hydrolysis reaction catalyst for coal hydrolysis is a substance represented by Formula 1 and Formula 2, or may be converted into the formula 1 or Formula 2 in water.

Μ I——S Η or

Formula two

In the formula,

"M" means metal, carbon, or silicon;

"S" indicates a hetero atom;

"L" represents one or more ligands;

"H" means hydrogen.

The method according to claim 1, wherein the hydrolysis of the coal is carried out in the presence of cellulose, and the ratio between the cellulose and the coal is between 1:100 and 1:1.

6. The method of claim 1 wherein the cellulose is cellulose present in pure cellulose, or a cellulose-containing material.

7. Process according to claim 6, characterized in that, in the case of cellulosic biomass, the total content of cellulose and hemicellulose is at least one third of the weight of coal.

8. Process according to claim 1, characterized in that the hydrogenation of the hydrolysate is carried out by catalytic hydrogenation or by catalytic transfer hydrogenation.

9. The method according to claim 8, wherein in the catalytic transfer hydrogenation reaction, the source of hydrogen is methanol, and the hydrogenation catalyst is porous copper magnesium aluminum metal oxide (Cu-PM0).

10. The method of claim 1 wherein said high calorific value hydrocarbon liquid fuel is selected from the group consisting of saturated hydrocarbons containing or not containing oxygen.