CN101993728A - Method for producing diesel by coal tar - Google Patents
Method for producing diesel by coal tar Download PDFInfo
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- CN101993728A CN101993728A CN2010105612453A CN201010561245A CN101993728A CN 101993728 A CN101993728 A CN 101993728A CN 2010105612453 A CN2010105612453 A CN 2010105612453A CN 201010561245 A CN201010561245 A CN 201010561245A CN 101993728 A CN101993728 A CN 101993728A
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- coal tar
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- aluminium silicate
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Abstract
The invention discloses a method for producing diesel by coal tar, in particular to a method for producing diesel by the hydrogenation of coal tar under the function of a Co and Mo based protecting agent. A fraction of below 370 DEG C is cut off after the coal tar is distilled at normal pressure, the hydrogenation refining is carried out under the function of the protecting agent and a catalyst, and a liquid-phase product is sent to a stripping tower to be stripped to obtain the diesel, wherein the protecting agent in the hydrogenation refining process comprises 3-8 wt% of MoO3, 2-5 wt% of CoO and the balance of aluminium silicate. The method has the advantages of simple operation, good hydrogenation reaction effect, good stability and lower cost, can be used for removing impurities of S, N, O and the like in the fraction of the coal tar, can ensure that aromatic hydrocarbon is saturated or isomerized, and can be massively applied to the fields of coal tar deep processing and diesel preparation.
Description
Technical field
The present invention relates to a kind of method of coal tar hydrogenating system diesel oil, relate to the method for coal tar hydrogenating system diesel oil under the effect of a kind of Co, Mo base protective material specifically.
Background technology
Along with the develop rapidly of world economy, industrial expansion such as automobile, aviation especially, the petroleum resources worsening shortages, and price constantly skyrockets.In China, the petroleum import ratio is increased sharply year by year, is the also increase thereupon of breach such as diesel oil of raw material with it.And the coal resources of China are abundant relatively, and through exploring, producing diesel oil with coal becomes a kind of trend, and in the prior art, DCL/Direct coal liquefaction or indirect liquefaction can output diesel oil, but the two Technology is quite complicated, and running cost and difficulty are bigger.
By-product coal tar in the Coal Chemical Industry process, production diesel oil also can be used.In general coal tar produce by coal carbonization, be divided into low-temperature pyrolysis, medium temperature carbonization and high temperature carbonization again, wherein the productive rate of coal tar is the highest in the low-temperature pyrolysis of coal, and the coal that is applicable to low-temperature pyrolysis is no close-burning non-coking coal, as brown coal or high-volatile bituminous coal, in China, these class coal reserves are abundant, be that coal tar is produced in low-temperature pyrolysis, and the basis of system diesel oil.The low-temperature pyrolysis process is simply more a lot of than coal gasification or direct liquefaction, and mild condition, if can make it to obtain reasonable use, then can become good diesel production source.CN88105117 discloses a kind of prescription and compound method thereof of fuel reagent replacing diesel, is to be raw material with coal tar, and through operations such as refining, distillation, emulsification, water mixing, purifications, academic title's fuel oil as oil fuel, but can not replace diesel oil.US4855037 has introduced a kind of Catalyst And Method of hydrogenation treatment for coal tar, coal tar after the hydrotreatment is used for delayed coking, this method mainly is by improving aperture, pore distribution and the metal component of catalyzer, and select suitable process conditions to improve the stability of catalyzer, this method mainly is the pre-treatment that is used for delayed coking, not production purpose product.In addition; need to add protective material in the hydrogenation process of coal tar system diesel oil, metallic impurity in the effective elimination oil product and solid particulate matter, and make in the raw material material appropriateness hydrogenation of easily coking; slow down the poisoning and the coking of Primary Catalysts, prolong the work-ing life of Primary Catalysts.Patent CN1147575C has invented a kind of method of coal tar system diesel oil; it is by the catalyst loading scheme of two sections gratings or three sections gratings; protective material, Hydrobon catalyst and dearomatization catalyst are added reaction system; obtain certain effect; but; this protectant effect is limited, can not make the maximizing efficiency of hydrogenation reaction.
Summary of the invention
The method of a kind of coal tar hydrogenating system diesel oil provided by the invention, described method is simple, hydrogenation reaction is effective, good stability, can remove impurity such as S, N in the coal tar fraction, O, can make the saturated or isomerization of aromatic hydrocarbons, cost is lower, can be widely used in coal tar deep processing and diesel oil preparation field.
For solving the problems of the technologies described above, technical scheme of the present invention is as follows:
A kind of method of coal tar hydrogenating system diesel oil; with the cut that cuts after the coal tar air distillation below 370 ℃; carry out hydrofining under protective material and catalyst action, liquid product is sent into stripping tower obtain diesel oil through stripping, protective material consists of the MoO of 3-8wt% in the unifining process
3, the CoO of 2-5wt%, all the other are pure aluminium silicate.
Hydrorefined reaction conditions is: temperature of reaction 350-370 ℃, and reaction pressure 6-12MPa, air speed 0.5-1.2h
-1, hydrogen to oil volume ratio is 800-1100.
Also can be provided with after the described hydrofining reaction and take off fragrant catalyzed reaction link, in order to remove aromatic hydrocarbons and heterocycle.
Described protectant volumetric usage is the 15-20% of protective material and catalyzer cumulative volume.
Described pure aluminium silicate aperture is 40-60nm.
The present invention has following advantage:
1. by adding described protective material, help the maximized hydrogenation reaction effect of improving, good stability, under the effect of hydrogenation catalyst and dearomatization catalyst, can remove impurity such as S, N in the coal tar fraction, O, make the saturated or isomerization of aromatic hydrocarbons, easy control of reaction conditions, and cost is lower, the diesel yield height;
2. support the component pure aluminium silicate in the protective material and have and promote heavy constituent cracking and isomerized function in the coal tar, and the aperture is that the microtexture of 40-60nm helps hydro carbons and reacts on its surface.
Embodiment
To help to understand the present invention by following embodiment, but not limit content of the present invention.
Embodiment 1
A kind of method of coal tar hydrogenating system diesel oil; with the cut that cuts after the coal tar air distillation below 370 ℃; carry out hydrofining under protective material and catalyst action, liquid product is sent into stripping tower obtain diesel oil through stripping, protective material consists of the MoO of 5.5wt% in the unifining process
3, the CoO of 3.5wt%, all the other are pure aluminium silicate, described pure aluminium silicate aperture is greatly between 40-60nm.
Hydrorefined reaction conditions is: 360 ℃ of temperature of reaction, reaction pressure 9MPa, air speed 1h
-1, hydrogen to oil volume ratio is 950.
Be provided with after the described hydrofining reaction and take off fragrant catalyzed reaction link, in order to remove aromatic hydrocarbons and heterocycle.
Described protectant volumetric usage is 17.5% of protective material and a catalyzer cumulative volume.
The yield of reaction gained diesel oil is 72%, and diesel oil character sees Table 1.
Embodiment 2
A kind of method of coal tar hydrogenating system diesel oil; with the cut that cuts after the coal tar air distillation below 370 ℃; carry out hydrofining under protective material and catalyst action, liquid product is sent into stripping tower obtain diesel oil through stripping, protective material consists of the MoO of 3wt% in the unifining process
3, the CoO of 5wt%, all the other are pure aluminium silicate, described pure aluminium silicate aperture is greatly between 40-60nm.
Hydrorefined reaction conditions is: 350 ℃ of temperature of reaction, reaction pressure 12MPa, air speed 1.2h
-1, hydrogen to oil volume ratio is 800.
Described protectant volumetric usage is 15% of protective material and a catalyzer cumulative volume.
The yield of reaction gained diesel oil is 65%, and diesel oil character sees Table 1.
Embodiment 3
A kind of method of coal tar hydrogenating system diesel oil; with the cut that cuts after the coal tar air distillation below 370 ℃; carry out hydrofining under protective material and catalyst action, liquid product is sent into stripping tower obtain diesel oil through stripping, protective material consists of the MoO of 8wt% in the unifining process
3, the CoO of 2wt%, all the other are pure aluminium silicate, described pure aluminium silicate aperture is greatly between 40-60nm.
Hydrorefined reaction conditions is: 370 ℃ of temperature of reaction, reaction pressure 6MPa, air speed 0.5h
-1, hydrogen to oil volume ratio is 1100.
Be provided with after the described hydrofining reaction and take off fragrant catalyzed reaction link, in order to remove aromatic hydrocarbons and heterocycle.
Described protectant volumetric usage is 20% of protective material and a catalyzer cumulative volume.
The yield of reaction gained diesel oil is 69%, and diesel oil character sees Table 1.
Embodiment 4
A kind of method of coal tar hydrogenating system diesel oil; with the cut that cuts after the coal tar air distillation below 370 ℃; carry out hydrofining under protective material and catalyst action, liquid product is sent into stripping tower obtain diesel oil through stripping, protective material consists of the MoO of 8wt% in the unifining process
3, the CoO of 5wt%, all the other are pure aluminium silicate, described pure aluminium silicate aperture is greatly between 40-60nm.
Hydrorefined reaction conditions is: 370 ℃ of temperature of reaction, reaction pressure 12MPa, air speed 0.5h
-1, hydrogen to oil volume ratio is 1000.
Be provided with after the described hydrofining reaction and take off fragrant catalyzed reaction link, in order to remove aromatic hydrocarbons and heterocycle.
Described protectant volumetric usage is 20% of protective material and a catalyzer cumulative volume.
The yield of reaction gained diesel oil is 70%, and diesel oil character sees Table 1.
Embodiment 5
A kind of method of coal tar hydrogenating system diesel oil; with the cut that cuts after the coal tar air distillation below 370 ℃; carry out hydrofining under protective material and catalyst action, liquid product is sent into stripping tower obtain diesel oil through stripping, protective material consists of the MoO of 5wt% in the unifining process
3, the CoO of 5wt%, all the other are pure aluminium silicate, described pure aluminium silicate aperture is greatly between 40-60nm.
Hydrorefined reaction conditions is: 370 ℃ of temperature of reaction, reaction pressure 12MPa, air speed 1h
-1, hydrogen to oil volume ratio is 900.
Be provided with after the described hydrofining reaction and take off fragrant catalyzed reaction link, in order to remove aromatic hydrocarbons and heterocycle.
Described protectant volumetric usage is 15% of protective material and a catalyzer cumulative volume.
The yield of reaction gained diesel oil is 68%, and diesel oil character sees Table 1.
Embodiment 6
A kind of method of coal tar hydrogenating system diesel oil; with the cut that cuts after the coal tar air distillation below 370 ℃; carry out hydrofining under protective material and catalyst action, liquid product is sent into stripping tower obtain diesel oil through stripping, protective material consists of the MoO of 6wt% in the unifining process
3, the CoO of 3wt%, all the other are pure aluminium silicate, described pure aluminium silicate aperture is greatly between 40-60nm.
Hydrorefined reaction conditions is: 370 ℃ of temperature of reaction, reaction pressure 10MPa, air speed 1h
-1, hydrogen to oil volume ratio is 900.
Be provided with after the described hydrofining reaction and take off fragrant catalyzed reaction link, in order to remove aromatic hydrocarbons and heterocycle.
Described protectant volumetric usage is 20% of protective material and a catalyzer cumulative volume.
The yield of reaction gained diesel oil is 70%, and diesel oil character sees Table 1.
Embodiment 7
A kind of method of coal tar hydrogenating system diesel oil; with the cut that cuts after the coal tar air distillation below 370 ℃; carry out hydrofining under protective material and catalyst action, liquid product is sent into stripping tower obtain diesel oil through stripping, protective material consists of the MoO of 4wt% in the unifining process
3, the CoO of 5wt%, all the other are pure aluminium silicate, described pure aluminium silicate aperture is greatly between 40-60nm.
Hydrorefined reaction conditions is: 370 ℃ of temperature of reaction, reaction pressure 8MPa, air speed 0.8h
-1, hydrogen to oil volume ratio is 1100.
Be provided with after the described hydrofining reaction and take off fragrant catalyzed reaction link, in order to remove aromatic hydrocarbons and heterocycle.
Described protectant volumetric usage is 20% of protective material and a catalyzer cumulative volume.
The yield of reaction gained diesel oil is 69%, and diesel oil character sees Table 1.
The character of table 1 diesel oil
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Density kg/m3 | 0.95 | 0.94 | 0.95 | 0.93 | 0.93 | 0.95 | 0.95 |
| Carbon residue wt% | 0.3 | 0.2 | 0.3 | 0.3 | 0.3 | 0.3 | 0.28 |
| Condensation point ℃ | -5 | -6 | -6 | -5 | -5 | -5 | -6 |
| IBP/10％ | 110/180 | 110/200 | 110/195 | 115/200 | 120/190 | 115/200 | 130/195 |
| 50％/90％ | 275/330 | 240/340 | 290/345 | 280/350 | 280/340 | 280/350 | 280/340 |
| FBP | 385 | 379 | 392 | 390 | 385 | 385 | 390 |
Claims (5)
1. the method for a coal tar system diesel oil; with the cut that cuts after the coal tar air distillation below 370 ℃; under protective material and catalyst action, carry out hydrofining; liquid product is sent into stripping tower obtain diesel oil, it is characterized in that protective material in the unifining process consists of the MoO of 3-8wt% through stripping
3, the CoO of 2-5wt%, all the other are pure aluminium silicate.
2. the method for coal tar system diesel oil according to claim 1 is characterized in that described hydrorefined reaction conditions is: temperature of reaction 350-370 ℃, and reaction pressure 6-12MPa, air speed 0.5-1.2h
-1, hydrogen to oil volume ratio is 800-1100.
3. the method for coal tar system diesel oil according to claim 1 and 2 is characterized in that also being provided with after the described hydrofining reaction and takes off fragrant catalyzed reaction link.
4. the method for coal tar system diesel oil according to claim 1 and 2 is characterized in that described protectant volumetric usage is the 15-20% of protective material and catalyzer cumulative volume.
5. the method for coal tar system diesel oil according to claim 1 is characterized in that described pure aluminium silicate aperture is 40-60nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105612453A CN101993728A (en) | 2010-11-26 | 2010-11-26 | Method for producing diesel by coal tar |
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| CN2010105612453A CN101993728A (en) | 2010-11-26 | 2010-11-26 | Method for producing diesel by coal tar |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089453A (en) * | 1990-06-25 | 1992-02-18 | Chevron Research And Technology Company | Hydroconversion catalyst and method for making the catalyst |
| CN1351130A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Hydrogenation process for preparing diesel oil from coal-tar oil |
| CN1464031A (en) * | 2002-06-07 | 2003-12-31 | 上海博申工程技术有限公司 | Coal tar hydrogenation process and catalyst therefor |
| CN101885984A (en) * | 2010-07-09 | 2010-11-17 | 中国科学院过程工程研究所 | Combined technology for producing clean fuel oil by hydrogenation of coal tar and catalyst thereof |
-
2010
- 2010-11-26 CN CN2010105612453A patent/CN101993728A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089453A (en) * | 1990-06-25 | 1992-02-18 | Chevron Research And Technology Company | Hydroconversion catalyst and method for making the catalyst |
| CN1351130A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Hydrogenation process for preparing diesel oil from coal-tar oil |
| CN1464031A (en) * | 2002-06-07 | 2003-12-31 | 上海博申工程技术有限公司 | Coal tar hydrogenation process and catalyst therefor |
| CN101885984A (en) * | 2010-07-09 | 2010-11-17 | 中国科学院过程工程研究所 | Combined technology for producing clean fuel oil by hydrogenation of coal tar and catalyst thereof |
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Application publication date: 20110330 |