CN102921462A - Preparation method and application method of catalyst with spongy iron as predecessor - Google Patents
Preparation method and application method of catalyst with spongy iron as predecessor Download PDFInfo
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- CN102921462A CN102921462A CN2011102293573A CN201110229357A CN102921462A CN 102921462 A CN102921462 A CN 102921462A CN 2011102293573 A CN2011102293573 A CN 2011102293573A CN 201110229357 A CN201110229357 A CN 201110229357A CN 102921462 A CN102921462 A CN 102921462A
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Abstract
The invention provides a preparation method and an application method of a catalyst with spongy iron as a predecessor. In the invention, the spongy iron which is adopted as a raw material reacts with a carbon monoxide gas in a catalyst preparation reactor to produce an iron-based catalyst. The obtained liquid carbonyl iron is directly pumped into a direct coal liquefaction reaction system or an oil-coal co-processing reaction system through a metering high-pressure pump, and there are no loss of the catalyst in a slurry and no generation of the air pollution or the hidden safety trouble caused by the carbonyl iron through adopting the application method provided by the invention.
Description
Technical field
The present invention relates to coal Direct Hydrogenation liquefaction field and oily coal refines the field altogether, more particularly, is a kind of preparation method of the coal Direct Hydrogenation liquefaction catalyst take sponge iron as predecessor, and application process.
Background technology
The reserves of coal are maximum in the primary energy, secondly are oil.Because oil is easy to processing, so consumption is huge, particularly China's economy has occurred since the rapid development, and the fuel oil for vehicles consumption increases day by day, and supply falls short of demand, and situation is frequently showed.On the other hand, the China's oil degree of self-sufficiency descends year by year, and externally interdependency constantly increases, and International Crude Oil rises steadily.So the fuel oil supply has become one of key factor of restriction China economic development.Short situation not only appears in oil supply, and the in poor quality phenomenon of residual crude oil is extensively admitted.The crude oil in poor quality shows as hydrogen content and constantly descends, and assorted constituent content progressively increases.Require in the more and more higher situation at fuel oil quality, hydrotreatment and hydrocracking become the indispensable link of PETROLEUM PROCESSING.The technology such as under these circumstances, coal liquefaction, oily coal refine are altogether arisen at the historic moment.
In the technical process relevant with coal direct liquefaction, generally adopt the compound of the metals such as zinc, tin, iron, cobalt, nickel, molybdenum as catalyst.Consider that from the Technological Economy angle ferrum-based catalyst is generally adopted.CN1109734C utilizes iron salt solutions and ammoniacal liquor reaction, preparation Fe (OH) exactly
3Or Fe (OH)
2Superfine catalyst.CN1274415C then utilizes molysite and alkaline solution that FeOOH is deposited on the pulverized coal particle surface, has further improved decentralization.But this catalyst in use all can run into solution and coal dust operating of contacts, further needs filtration, drying etc., has not only increased energy consumption, and has formed a certain amount of waste liquid, and is very unfavorable for large-scale production.
CN101020834A discloses and has a kind ofly made the coal liquefaction method of catalyst based on iron pentacarbonyl, adds catalyst and fully mix in hydrogen supply dissolvent, and coal dust is mixed with the hydrogen supply dissolvent that contains catalyst, stirs to get coal slurry; Then coal slurry is imported in the high-pressure stirring reactor, carry out hydrogenation reaction.
Said method can use fully at the autoclave device in laboratory.But, industrial, coal slurry is hot existence in head tank, the coal slurry tank that refines altogether of oily coal particularly, temperature are between 50-150 ℃, and about 102 ℃ of the boiling point of iron pentacarbonyl, the iron pentacarbonyl Evaporation Phenomenon will appear inevitably near this temperature, not only affect catalyst content in the slurries, and because iron pentacarbonyl toxicity is very large, environment is caused certain pollution.In addition because iron pentacarbonyl is volatile, virose dangerous goods, loading and unloading, transportation are required very harsh, so there is certain potential safety hazard in the on-the-spot iron pentacarbonyl that directly uses.
Summary of the invention
To be solved by this inventionly be, when directly using poisonous, volatile iron pentacarbonyl as the DCL/Direct coal liquefaction catalyst in the prior art, exist in the slurries catalyst content impaired, and the problem such as environmental pollution.
The preparation method of the catalyst take sponge iron as predecessor provided by the invention comprises:
(1) sponge iron and hydrogen react in catalyst preparation reactor, and with imurity-removal, reaction temperature is 200-800 ℃, and the volume space velocity of hydrogen is 0.05-1.0h
-1, reaction pressure is 0.1-0.2MPa,
(2) hydrogen is switched to CO gas, sponge iron and carbon monoxide react, and the volume space velocity of carbon monoxide is 0.5-5.0h
-1, reaction temperature is 100-300 ℃, reaction pressure is 5-20MPa,
(3) effluent of step (2) catalyst preparation reactor gained obtains liquid carbonyl iron through cooling, separation, and catalyst preparation reactor effluent chilling temperature is 1-90 ℃.
Hydrogen purity is greater than 60% in the described step (1), and reaction temperature is 300-700 ℃.Under higher hydrogen gas air speed, can adopt the operation of hydrogen endless form.
After hydrogen content in the exit gas of catalyst preparation reactor is stable, cut off hydrogen gas in the described step (2), with the catalyst preparation reactor cooling, then pass into CO gas.
Described step (2) reaction temperature is 130-220 ℃, and the carbon monoxide volume content is greater than 80% in the reacting gas.
Chilling temperature is 10-60 ℃ in the described step (3).
Step (3) is also separated and is obtained unreacted CO gas, and described CO gas is through recycle compressor return catalizer preparation feedback device.
The application process of above-mentioned any one preparation method's gained catalyst provided by the invention through the metering high-pressure pump, directly enters the DCL/Direct coal liquefaction reaction system or oily coal refines reaction system altogether with the liquid carbonyl iron of described step (3) gained.
The addition of liquid carbonyl iron, take the coal that processes raw material as benchmark, the mass percent of iron is 0.3%-1.5%, the mass percent of preferred iron is 0.3%-0.9%.
When adding the liquid carbonyl iron catalyst, can also refine altogether reaction system adding molybdate compound to DCL/Direct coal liquefaction reaction system or oily coal, iron/molybdenum mass ratio is 50-200: 1.
When adding the liquid carbonyl iron catalyst, also refine altogether reaction system adding elemental sulfur to DCL/Direct coal liquefaction reaction system or oily coal, in mass, the addition of elemental sulfur is 1-3 times of iron.
DCL/Direct coal liquefaction reaction system or oily coal refine the operating temperature of reaction system altogether between 390-460 ℃, and reaction pressure is between 15-20MPa.
The present invention with the carbon monoxide gas precursor reactant, produces ferrum-based catalyst take sponge iron as raw material in catalyst preparation reactor.High-pressure pump is directly squeezed into the DCL/Direct coal liquefaction reaction system to the liquid carbonyl iron of gained or oily coal refines reaction system altogether through measuring, adopt method provided by the invention, there is not the impaired situation of catalyst content in the slurries, can not occur to cause any air pollution and potential safety hazard because of carbonyl iron yet.
Description of drawings
Accompanying drawing is the schematic diagram of preparation method and application's method of the catalyst take sponge iron as predecessor provided by the present invention.
The specific embodiment
Below by accompanying drawing method provided by the invention is further described, but not thereby limiting the invention.
As shown in drawings, the hydrogen from pipeline 2 passes into the catalyst preparation reactor 3 of having loaded sponge iron, air in the displacer.Then catalyst preparation reactor 3 temperature are raised to reduction reaction temperature, continue to pass into hydrogen, detect exit gas and form, when the hydrogen content substantially constant of exit gas, close hydrogen gas lines 2, allow simultaneously catalyst preparation reactor 3 coolings.When catalyst preparation reactor 3 temperature drop to reaction temperature, pass into CO gas by pipeline 1, and pressure is raised to reaction pressure.After cooler 4 coolings, enter together separator 5 from catalyst preparation reactor 3 mixture out, carry out gas-liquid separation.Separating obtained liquid carbonyl iron catalyst mixes with a certain proportion of hydrogen from pipeline 10 after high-pressure metering pump 7 pressurization, through nozzle atomization with mix from the high-pressure coal slurry of pipeline 11, this mixture enters from hydrogenation liquefaction reactor 6 bottoms together and carries out catalytic hydrogenation reaction, and products therefrom is removed the after-treatment systems such as cooling, separation by pipeline 12.The unreacted CO gas that separator 5 is separated converges after circulator 9 superchargings with from the CO gas of pipeline 1, and is recycling.The catalyst ratio that measuring pump 7 controls add to the catalytic hydrogenation system.
The following examples will be further described method of the present invention, but not thereby limiting the invention.
According to flow process shown in the accompanying drawing, catalyst is prepared in accordance with the following steps:
(1) sponge iron and hydrogen react in catalyst preparation reactor, and with imurity-removal, reaction temperature is 600 ℃, and the volume space velocity of hydrogen is 0.15h
-1, reaction pressure is 0.1MPa, (2) are detected exit gas and are formed, and when the hydrogen content substantially constant of exit gas, close hydrogen gas lines, allow simultaneously catalyst preparation reactor be cooled to 160 ℃.Hydrogen is switched to CO gas, and sponge iron and carbon monoxide react, and the volume space velocity of carbon monoxide is 1.2h
-1, reaction temperature is 160 ℃, reaction pressure is 17MPa, (3) after the cooler cooling, enter together separator from catalyst preparation reactor mixture out, carry out gas-liquid separation, obtain liquid carbonyl iron, catalyst preparation reactor effluent chilling temperature is 35 ℃.
Embodiment 1
The liquid carbonyl iron catalyst of preparation gained mixes with hydrogen after the high-pressure metering pump pressurization, and through nozzle atomization, the carbonyl iron catalyst is through measuring pump control flow 8.4g/h, and the atomizing hydrogen gas rate is 800Nml/h.
The coal (property of coal sees Table 1, and oil properties sees Table 2) that contains coal 40% is pressed the charging of 1.2kg/h speed, is pressurized to 18MPa through coal slurry pump, mixes hydrogen gas rate 700NL/h with hydrogen partial first.Afterwards with the atomizing catalyst mix, be preheating to 450 ℃ from reactor bottom enter begin the reaction.450 ℃ of reactor operating temperatures, operating pressure 18MPa, reactor are the cavity reactor, liquid hourly space velocity (LHSV) is 0.7h
-1Press the Mass Calculation of iron in the catalyst, its amount is 0.5% of coal in the hydrogenation liquefaction raw material.When adding the liquid carbonyl iron catalyst, also add molybdate compound to reaction system, wherein iron/molybdenum mass ratio is 100, also adds elemental sulfur to reaction system, in mass, the addition of elemental sulfur is 2.5 times of iron.Reaction the results are shown in Table 3 by cooling, gas-liquid separation, sample analysis.
Embodiment 2
Other condition is identical with embodiment 1, and the carbonyl iron catalyst of preparation is 16.8g/h through measuring pump control flow, and experimental result sees Table 2.
Table 1
Annotate:
Ad represents air-dried basis;
D represents dry base;
Daf represents dry ash free basis.
Table 2
| Analysis project | Shengli crude |
| 20 ℃ of density, kg/m 3 | 956.8 |
| 80 ℃ of viscosity, mm 2/s | 183.5 |
| Mechanical admixture, % (weight) | 0.036 |
| Four components | |
| Saturated hydrocarbons, % (weight) | 32.4 |
| Aromatic hydrocarbons, % (weight) | 26.7 |
| Colloid, % (weight) | 39.2 |
| Asphalitine, % (weight) | 1.7 |
| Element forms | |
| C | 84.98 |
| H | 11.66 |
| N | 1.04 |
| S | 2.00 |
| O | 1.54 |
| Add up to | 101.22 |
| Tenor | |
| Fe，mg/kg | 19.2 |
| Ni，mg/kg | 31.0 |
| V，mg/kg | 2.7 |
| Na，mg/kg | 19.4 |
| Ca，mg/kg | 36.0 |
| Boiling range | |
| Initial boiling point, ℃ | 188 |
| 5％，℃ | 311 |
| 10％，℃ | 353 |
| 30％，℃ | 469 |
| The distillation end point yield, % | 41.8 |
| The distillation end point temperature, ℃ | 513 |
Table 3
| Embodiment 1 | Embodiment 2 | |
| Reaction condition | ||
| Temperature, ℃ | 450 | 450 |
| Pressure, MPa | 18.0 | 18.0 |
| Slurry solid content, % by weight | 40 | 40 |
| Catalytic amount, % by weight | 0.5 | 1.0 |
| Iron/molybdenum mass ratio, | 100 | 100 |
| Reaction result | ||
| Gas yield, % by weight | 11 | 10 |
| The liquefaction oil productive rate, % by weight | 69 | 70 |
| The slurry oil productive rate, % by weight | 20 | 20 |
| The coal conversion ratio, % | 92.1 | 92.3 |
| The hydrogen consumption, % | 4.5 | 4.6 |
Claims (12)
1. the preparation method of the catalyst take sponge iron as predecessor comprises:
(1) sponge iron and hydrogen react in catalyst preparation reactor, and with imurity-removal, reaction temperature is 200-800 ℃, and the volume space velocity of hydrogen is 0.05-1.0h
-1, reaction pressure is 0.1-0.2MPa,
(2) hydrogen is switched to CO gas, sponge iron and carbon monoxide react, and the volume space velocity of carbon monoxide is 0.5-5.0h
-1, reaction temperature is 100-300 ℃, reaction pressure is 5-20MPa,
(3) effluent of step (2) catalyst preparation reactor gained obtains liquid carbonyl iron through cooling, separation, and catalyst preparation reactor effluent chilling temperature is 1-90 ℃.
2. according to preparation method claimed in claim 1, it is characterized in that hydrogen purity is greater than 60% in the described step (1), reaction temperature is 300-700 ℃.
3. according to preparation method claimed in claim 1, it is characterized in that, after hydrogen content in the exit gas of catalyst preparation reactor is stable, cut off hydrogen gas in the described step (2), with the catalyst preparation reactor cooling, then pass into CO gas.
4. according to preparation method claimed in claim 1, it is characterized in that described step (2) reaction temperature is 130-220 ℃, the carbon monoxide volume content is greater than 80% in the reacting gas.
5. according to preparation method claimed in claim 1, it is characterized in that chilling temperature is 10-60 ℃ in the described step (3).
6. according to preparation method claimed in claim 1, it is characterized in that step (3) is also separated and obtained unreacted CO gas, described CO gas is through recycle compressor return catalizer preparation feedback device.
7. the application process of any one preparation method's gained catalyst of claim 1-6 is characterized in that, the liquid carbonyl iron of described step (3) gained directly enters the DCL/Direct coal liquefaction reaction system or oily coal refines reaction system altogether through the metering high-pressure pump.
8. according to application process claimed in claim 7, it is characterized in that, the addition of liquid carbonyl iron, take the coal that processes raw material as benchmark, the mass percent of iron is 0.3%-1.5%.
9. according to application process claimed in claim 7, it is characterized in that, the addition of liquid carbonyl iron, take the coal that processes raw material as benchmark, the mass percent of iron is 0.3%-0.9%.
10. according to application process claimed in claim 7, it is characterized in that when adding the liquid carbonyl iron catalyst, also refine altogether reaction system adding molybdate compound to DCL/Direct coal liquefaction reaction system or oily coal, iron/molybdenum mass ratio is 50-200: 1.
11., it is characterized in that when adding the liquid carbonyl iron catalyst, also refine altogether reaction system adding elemental sulfur to DCL/Direct coal liquefaction reaction system or oily coal, in mass, the addition of elemental sulfur is 1-3 times of iron according to application process claimed in claim 7.
12., it is characterized in that DCL/Direct coal liquefaction reaction system or oily coal refine the operating temperature of reaction system altogether between 390-460 ℃ according to application process claimed in claim 7, reaction pressure is between 15-20MPa.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101209862A (en) * | 2007-12-25 | 2008-07-02 | 金川集团有限公司 | Method for preparing carbonyl iron |
| CN100556990C (en) * | 2007-03-10 | 2009-11-04 | 江苏天一超细金属粉末有限公司 | Make the coal liquefaction method of catalyzer based on pentacarbonyl iron |
| CN101696038A (en) * | 2009-10-26 | 2010-04-21 | 江西悦安超细金属有限公司 | Method for preparing carbonyl iron powder in high-pressure circulating way |
| CN101927167A (en) * | 2010-06-23 | 2010-12-29 | 煤炭科学研究总院 | Compound coal tar hydrogenation catalyst and preparation method thereof |
-
2011
- 2011-08-11 CN CN2011102293573A patent/CN102921462A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100556990C (en) * | 2007-03-10 | 2009-11-04 | 江苏天一超细金属粉末有限公司 | Make the coal liquefaction method of catalyzer based on pentacarbonyl iron |
| CN101209862A (en) * | 2007-12-25 | 2008-07-02 | 金川集团有限公司 | Method for preparing carbonyl iron |
| CN101696038A (en) * | 2009-10-26 | 2010-04-21 | 江西悦安超细金属有限公司 | Method for preparing carbonyl iron powder in high-pressure circulating way |
| CN101927167A (en) * | 2010-06-23 | 2010-12-29 | 煤炭科学研究总院 | Compound coal tar hydrogenation catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王炳根等: "羰基铁粉的热处理", 《四川冶金》 * |
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Application publication date: 20130213 |