Hydrogenation process for coal direct liquefaction circulation solvent

Abstract

The invention adopts a catalyst grading technology and installs adequate chemical reaction environment to carry out incompletely saturated hydrogenation in a mild technological condition, which not only mildly hydrogenates the unsaturated compound in dissolvent, but also mildly hydrogenates the saturated compound. The affected compounds of the hydrogenated dissolvent reach even degree of unsaturation on molecular structure, which improves transferable hydrogen content of molecule, accordingly the free hydrogen(-H) released by cycle dissolvent just can meet the need of hydrogen consumption of direct liquefaction of brown coal in a mild technological condition. The invention can simplify the industrial process of lignite liquification and solvent hydrogenation, reduce the device requirement, and save investment and operating cost.

Description

technical field

[0001] The invention relates to a hydrogenation method of a coal liquefaction solvent, in particular to a hydrogenation process of a lignite direct liquefaction circulating solvent. Background technique

[0002] The direct coal liquefaction method generally involves catalytic hydrogenation of coal and solvent oil under high temperature (400-500°C) and high-pressure (10.0-30.0MPa) conditions to generate a liquid fuel product with a high hydrogen-carbon ratio, which is used to supplement and replace Increasing shortage of petroleum fuel products. In the various existing coal direct liquefaction processes, some of them have carried out hydrogenation treatment on the solvent, so that the solvent has a certain hydrogen-donating effect. For example, Exxon's hydrogen-donating solvent (EDS) process and Japan's NEDOL process use fixed-bed hydrogenation technology to hydrogenate circulating solvents, and Germany's IGOR + Process and Chinese coal direct liquefaction p...

Examples

Embodiment 1～4

[0028] The self-made circulating solvent pre-hydrogenation special catalyst YZC-01 and the main hydrogenation special catalyst ZZC-02 were respectively loaded in two series-connected 600ml reactors according to the volume ratio of 1:1, and the hydrogenation test was carried out on the lignite liquefaction circulating solvent. The test conditions are shown in Table 1, and the comparison of raw oil and product properties is shown in Table 2.

[0029] Example

1

2

3

4

pressure, MPa

9.6

7.1

10.8

8.2

Inverse temperature, ℃

292

301

311

321

Secondary reaction temperature, ℃

323

341

350

360

Airspeed, h -1

0.3

0.2

0.25

0.25

Hydrogen oil ratio, v / v

65

85

95

130

[0030]The data in table 1 shows that in four examples, the highest pressure is 10.8MPa...

Embodiment 5

[0038] Example 5 uses the mixed products of Examples 1-4 as solvent to carry out lignite hot-melt catalysis test, and compares it with Example 6 which uses non-hydrogenated circulating solvent to carry out lignite hot-melt catalysis test. The tests were all carried out in an autoclave with a volume of 2000ml. After the reaction materials were installed, pressurize to the reaction pressure with nitrogen, control the pressure to be constant, and heat up the reaction under stirring. The test results are shown in Table 3.

[0039] Example

[0040] The data in Table 3 show that under the same ratio of agent to coal and reaction conditions, the non-hydrogenation solvent basically has no hydrogen donation effect, and the solvent undergoes condensation and coking reactions with the unsaturated substances produced by the pyrolysis of coal powder under the action of high temperature and pressure. It leads to the decrease of liquid and the increase of solid, except that the wate...

technical field

[0001] The invention relates to a hydrogenation method of a coal liquefaction solvent, in particular to a hydrogenation process of a lignite direct liquefaction circulating solvent. Background technique

[0002] The direct coal liquefaction method generally involves catalytic hydrogenation of coal and solvent oil under high temperature (400-500°C) and high-pressure (10.0-30.0MPa) conditions to generate a liquid fuel product with a high hydrogen-carbon ratio, which is used to supplement and replace Increasing shortage of petroleum fuel products. In the various existing coal direct liquefaction processes, some of them have carried out hydrogenation treatment on the solvent, so that the solvent has a certain hydrogen-donating effect. For example, Exxon's hydrogen-donating solvent (EDS) process and Japan's NEDOL process use fixed-bed hydrogenation technology to hydrogenate circulating solvents, and Germany's IGOR + Process and Chinese coal direct liquefaction p...

Examples

Embodiment 1～4

[0028] The self-made circulating solvent pre-hydrogenation special catalyst YZC-01 and the main hydrogenation special catalyst ZZC-02 were respectively loaded in two series-connected 600ml reactors according to the volume ratio of 1:1, and the hydrogenation test was carried out on the lignite liquefaction circulating solvent. The test conditions are shown in Table 1, and the comparison of raw oil and product properties is shown in Table 2.

[0029] Example

1

2

3

4

pressure, MPa

9.6

7.1

10.8

8.2

Inverse temperature, ℃

292

301

311

321

Secondary reaction temperature, ℃

323

341

350

360

Airspeed, h -1

0.3

0.2

0.25

0.25

Hydrogen oil ratio, v / v

65

85

95

130

[0030]The data in table 1 shows that in four examples, the highest pressure is 10.8MPa...

Embodiment 5

[0038] Example 5 uses the mixed products of Examples 1-4 as solvent to carry out lignite hot-melt catalysis test, and compares it with Example 6 which uses non-hydrogenated circulating solvent to carry out lignite hot-melt catalysis test. The tests were all carried out in an autoclave with a volume of 2000ml. After the reaction materials were installed, pressurize to the reaction pressure with nitrogen, control the pressure to be constant, and heat up the reaction under stirring. The test results are shown in Table 3.

[0039] Example

[0040] The data in Table 3 show that under the same ratio of agent to coal and reaction conditions, the non-hydrogenation solvent basically has no hydrogen donation effect, and the solvent undergoes condensation and coking reactions with the unsaturated substances produced by the pyrolysis of coal powder under the action of high temperature and pressure. It leads to the decrease of liquid and the increase of solid, except that the wate...

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