CN104974793A - Method for grading catalysts during hydrogenation of medium-low-temperature coal tar - Google Patents
Method for grading catalysts during hydrogenation of medium-low-temperature coal tar Download PDFInfo
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Abstract
The invention relates to a method for grading catalysts during hydrogenation of medium-low-temperature coal tar. A hydrogenation process comprises the following steps: mixing raw coal tar and hydrogen, and allowing the mixture to enter a No.1 protection reactor, a No.2 refining reactor, a No.3 modification reactor and a high-low separation system in sequence to finish a hydrogenation refining stage; allowing the separated liquid to enter a fractionating system, and allowing the obtained tail coal tar to enter a No.4 refining reactor, a No.5 cracking reactor and the high-low separation system to finish a hydrogenation and cracking stage and obtain a light fuel. Through optimization of a combination mode of the catalysts, the activity of the catalysts is further improved, and the service life of the catalysts and the operation cycle of devices are prolonged on the premise of ensuring the quality of the fuel product.
Description
Technical field
To the present invention relates in one grading method of catalyst in coalite tar hydrogenation process, belong to technical field of coal chemical industry.
Background technology
Coal tar is a kind of poor quality oil produced in dry distillation of coal process, and its complicated components, containing a large amount of heteroatomss.At present, utilize the best method of coal tar to be carried out refinement treatment, the oil after hydrogenation is as the charging of hydrocracking.In treating process, in order to reach refining effect, need the catalyzer of difference in functionality to combine.And the suitable grating ratio of different catalysts is not only the guarantee of target product quality, also farthest can give play to the Characteristic and function of each catalyzer.Therefore catalyst grade facing-up is studied carefully and is had great significance in coal tar refining process.
Existing result of study provides the grading method of catalyst adopted in multiple coal tar hydrogenating process, as: CN102899082A discloses a kind of Hydrobon catalyst grading method of coal tar deep purifying, give full play to the demetalization of catalyzer, desulfurization and denitrification activity, there is very high impurity removal percentage, but the octane value of products therefrom and cetane value lower.CN102161909A discloses a kind of catalyst loading method for preparing fuel oil with coal oil hydrogenation.But it is more to relate to reactor, cost is high, and maintenance workload is large.In addition, some hydrofinings for coal tar purification, the research of cracking catalyst grading method is also had, though have higher transformation efficiency, but the intensity of catalyzer is undesirable, active effect is relatively bad, and the finishing agent of this scheme only can run 1.5 years, and cracking agent is 1.0 years.
Summary of the invention
In order to solve the problem, the invention provides grading method of catalyst in a kind of middle coalite tar hydrogenation process newly, by to catalyst combination method optimizing, under the prerequisite ensureing fuel oil products quality, further raising catalyst activity, work-ing life of extending catalyst and device running period.
To achieve these goals, the present invention adopts following technical scheme:
Grading method of catalyst in a kind of coal tar hydrogenating process, its hydrogenation technique is: enter No. 1 guard reactor, No. 2 refining reaction devices, No. 3 reforming reactors, height separation systems after stock oil mixes with hydrogen successively, complete hydrofinishing state; Liquid after separation enters fractionating system, and gained tail oil enters No. 4 refining reaction devices, No. 5 cracking cases, height separation systems more successively, completes hydrocracking stage, obtains light-weight fuel oil;
Wherein, each catalyst reactor grating is specific as follows:
The described No. 1 each bed of guard reactor and catalyst loading ratio are: the metal remover of the first bed filling 55-65V%, the ZDL-T1 agent of the second bed filling 20-25V%, the ZDL-T2 agent of the 3rd bed filling 15-20V%;
The described No. 2 each beds of refining reaction device and catalyst loading ratio are: the ZDL-J1 agent of the first bed filling 15-20V%, the second bed filling ZDL-J1 agent of 15-20V% and ZDL-J2 agent of 19-21V%, the ZDL-J2 agent of the 3rd bed filling 44-46V%;
The described No. 3 each beds of reforming reactor and catalyst loading ratio are: the ZDL-G1 agent of the first bed filling 20-25V%, the second bed filling ZDL-G1 agent of 15-21V% and ZDL-G2 agent of 18-25V%, the ZDL-G2 agent of the 3rd bed filling 35-41V%;
The described No. 4 each beds of refining reaction device and catalyst loading ratio are: the ZDL-J1 agent of the first bed filling 15-20V%, the second bed filling ZDL-J1 agent of 15-19V% and ZDL-J2 agent of 20-23V%, the ZDL-J2 agent of the 3rd bed filling 39-45V%;
The described No. 5 each beds of cracking case and catalyst loading ratio are: the ZDL-L1 agent of the first bed filling 22-25V%, the second bed filling ZDL-L1 agent of 15-20V% and the ZDL-L2 agent of 10-12V%, the 3rd bed filling ZDL-L1 agent of 10-13V% and the ZDL-L2 agent of 12-15V%, the ZDL-L2 agent of the 4th bed filling 18-25V%.
As the preferred embodiment of the present invention, the described No. 1 each bed of guard reactor and catalyst loading ratio are: the metal remover of the first bed filling 60V%, the ZDL-T1 agent of the second bed filling 20V%, the ZDL-T2 agent of the 3rd bed filling 20V%;
The described No. 2 each beds of refining reaction device and catalyst loading ratio are: the ZDL-J1 agent of the first bed filling 20V%, the second bed filling ZDL-J1 agent of 15V% and ZDL-J2 agent of 20V%, the ZDL-J2 agent of the 3rd bed filling 45V%;
The described No. 3 each beds of reforming reactor and catalyst loading ratio are: the ZDL-G1 agent of the first bed filling 25V%, the second bed filling ZDL-G1 agent of 15V% and ZDL-G2 agent of 25V%, the ZDL-G2 agent of the 3rd bed filling 35V%;
The described No. 4 each beds of refining reaction device and catalyst loading ratio are: the ZDL-J1 agent of the first bed filling 20V%, the second bed filling ZDL-J1 agent of 15V% and ZDL-J2 agent of 20V%, the ZDL-J2 agent of the 3rd bed filling 45V%;
The described No. 5 each beds of cracking case and catalyst loading ratio are: the ZDL-L1 agent of the first bed filling 25V%, the mixture of the second bed filling ZDL-L1 agent of 15V% and the ZDL-L2 agent of 10V%, the 3rd bed filling ZDL-L1 agent of 10V% and the ZDL-L2 agent of 15V%, the ZDL-L2 agent of the 4th bed filling 25V%.
In above-mentioned grading method of catalyst, the concrete composition of each catalyzer is as follows:
Described ZDL-T1 agent component is: with catalyst weight, and carrier MCM-41 mesopore molecular sieve accounts for 70-80%, active ingredient MoO
3account for 7-9%, auxiliary agent NiO, P
2o
58-10%, 2-7% respectively; Its pore volume 1.0-1.2mL/g, specific surface area 140-160m
2/ g, bore dia is that 25-100nm, 30-50nm account for more than 80V%.
Described ZDL-T2 agent component is: with catalyst weight, carrier A l
2o
370-80% is accounted for, active ingredient MoO with MCM-41 mesopore molecular sieve
3account for 7-9%, auxiliary agent NiO, P
2o
58-10%, 2-7% respectively; Its pore volume 1.0-1.2mL/g, specific surface area 140-160m
2/ g, bore dia is that 25-100nm, 20-40nm account for more than 80V%.
Described ZDL-J1 agent component is: with catalyst weight, the complex carrier that carrier is made up of titanium dioxide and aluminum oxide, and wherein titanium dioxide accounts for 3-5%, alumina catalyst support accounts for 60-67%, active ingredient MoO
3, WO
3account for 3-9%, 5-10% respectively, auxiliary agent NiO, P
2o
5, C
o2o
3, MgO, ruthenium salt accounts for 4-5%, 6.5-8%, 1-3%, 2-7%, 2-3% respectively; Its pore volume 0.5-0.7mL/g, specific surface area 165-175m
2/ g, bore dia is that 8-100nm, 20-40nm account for more than 80V%.
Described ZDL-J2 agent component is: with catalyst weight, the complex carrier that carrier is made up of titanium dioxide and aluminum oxide, and wherein titanium dioxide accounts for 3-5%, aluminum oxide accounts for 62-65%, active ingredient MoO
3, WO
3account for 4-8%, 4-6% respectively, auxiliary agent NiO, P
2o
5, C
o2o
3, MgO, ruthenium salt accounts for 5-7%, 5-6%, 2-5%, 2-4%, 3-4% respectively; Its pore volume 0.6-0.8mL/g, specific surface area 160-180m
2/ g, bore dia is that 9-100nm, 15-25nm account for more than 80V%.
Described ZDL-G1 agent component is: with catalyst weight, alumina catalyst support accounts for 65-75%, and Zn, Mg and aluminum oxide react the carrier Zinc aluminate that generates spinel structure or magnesium aluminate accounts for 5-7%, active ingredient NiO, WO
3, MoO
3account for 5-8% respectively, 2-8%, 6-20%; Its pore volume 0.58-0.8mL/g, specific surface area 310-330m
2/ g, bore dia is that 8-100nm, 20-40nm account for more than 80V%.
Described ZDL-G2 agent component is: with catalyst weight, alumina catalyst support accounts for 60-65%, and Zn, Mg and aluminum oxide react the carrier Zinc aluminate that generates spinel structure or magnesium aluminate 6-8%, active ingredient NiO, WO
3, MoO
3account for 5-10% respectively, 5-8%, 17-22%; Its pore volume 0.62-0.9mL/g, specific surface area 300-330m2/g, bore dia is that 7-100nm, 15-25nm account for more than 80V%.
Described ZDL-L1 agent component is: with catalyst weight, alumina catalyst support accounts for 60-65% and silicon-dioxide accounts for 4-6%, and Zn, Mg and aluminum oxide react the carrier Zinc aluminate or magnesium aluminate 5-7%, active ingredient WO that generate spinel structure
3, MoO
3account for 3-5%, 6-15% respectively, auxiliary agent NiO accounts for 8-10%, C
o2o
3account for 7-9%; Its pore volume 0.61-0.9mL/g, specific surface area 330-350m
2/ g, bore dia is that 8-100nm, 20-40nm account for more than 80V%.
Described ZDL-L2 agent component is: with catalyst weight, alumina catalyst support accounts for 60-65%, and silicon-dioxide accounts for 6-8%, and Zn, Mg and aluminum oxide react the Zinc aluminate or magnesium aluminate 8-10%, active ingredient WO that generate spinel structure
3, MoO
3account for 8-10%, 5-15% respectively, auxiliary agent NiO accounts for 3-5%, C
o2o
3account for 3-5%; Its pore volume 0.57-0.7mL/g, specific surface area 320-330m
2/ g, bore dia is that 6-100nm, 15-25nm account for more than 80V%.
The hydrogenation technique reaction conditions adopting above-mentioned catalyzer to arrange is as follows:
Hydrofinishing state: pressure is 8-15MPa, hydrogen to oil volume ratio 800-1800:1 (V/V), No. 1 guard reactor temperature of reaction is 230-280 DEG C, cumulative volume air speed 1.2-1.3h
-1, No. 2 refining reaction device temperature of reaction are 330-380 DEG C, cumulative volume air speed 0.8-0.9h
-1, No. 3 reforming reactor temperature of reaction are 360-390 DEG C, cumulative volume air speed 0.8-0.9h
-1;
Hydrocracking stage: pressure is 15-19MPa, hydrogen to oil volume ratio 1500-2800:1 (V/V), No. 4 refining reaction device temperature of reaction are 330-380 DEG C, cumulative volume air speed 0.3-1.1h
-1, No. 5 cracking case temperature of reaction are 370-390 DEG C, cumulative volume air speed 1.0-1.5h
-1.
Present invention applicant finds through great many of experiments, if air speed is too high, catalyst deactivation speed is accelerated; Air speed is too small, and the oil product residence time is long, and gas recovery ratio increases, but the time that product stops in beds is longer, and the chance of comprehensive coking also increases thereupon.Therefore, the application determines best volume space velocity for the catalyzer grading distribution scheme in each reactor.
The technique effect that scheme of the present invention obtains is as follows:
1) adopt grading method of catalyst of the present invention, the deviating from step by step of the metal in coal tar can be made, be evenly distributed in whole beds, avoid depositing in a certain spatial concentration, the ramp-up rate of demanding a lower price of reactor is effectively delayed.
2) adopt catalyzer grading distribution scheme of the present invention, bed radial temperature difference is little, makes chemical reaction process be in ideal efficient state, effectively can solve the reaction engineering problems such as back-mixing, channel, radial temperature difference be large.
3) support of the catalyst of the present invention has the porous material of enough physical strengths, bears skeleton and increases specific activity surface, improves the heat conductivility of catalyzer and increases the toxin immunity of catalyzer.
4) carrier of catalyzer of the present invention adopts TiO
2the TiO of modulation
2/ r-Al
2o
3complex carrier, can obviously improve catalyst activity component MoO
3dispersion state, surface tissue and catalytic performance.TiO
2add and can weaken MoO
3with r-Al
2o
3between interaction, promote MoO
3reduction, improve the hydrodesulfurization activity of catalyzer.
5) Zn, Mg and aluminum oxide react the Zinc aluminate or magnesium aluminate that generate spinel structure, have stronger tetrahedral coordination tendency, suppress the generation of inactive isolated tetrahedron tungsten (or molybdenum) species and nickel aluminate in the process of hydrogenation.
6) at hydrofinishing state and hydrocracking stage, ruthenium salt is joined in cobalt, molybdenum, aluminium oxide catalyst as auxiliary agent, make its real through engineering approaches, HDS, HYD performance of catalyzer can be significantly improved.
7) grading method of catalyst of the present invention can process coal-tar middle oil, coalite tar, middle coalite tar, shale oil, wax oil; Obtain meeting the stock oil entering fixed bed by proportioning.
Grading method of catalyst of the present invention effectively improves the activity of catalyzer, and cracking rate is up to 95%; And under the prerequisite ensureing fuel oil products quality, improve catalyst activity further, work-ing life of extending catalyst and device running period, thus reduce device quantity and maintenance load, reduce production cost.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Catalyzer grating concrete scheme in coalite tar hydrogenation process in embodiment 1
By coal-tar middle oil, coalite tar, middle coalite tar, shale oil according to the mixing of weight ratio 5:7:3:2 ratio, mixed stock oil performance index are as shown in table 1.
Table 1
Hydrogenation technique is: enter No. 1 guard reactor, No. 2 refining reaction devices, No. 3 reforming reactors, height separation systems after stock oil mixes with hydrogen successively, complete hydrofinishing state; Liquid after separation enters fractionating system, and gained tail oil enters No. 4 refining reaction devices, No. 5 cracking cases, height separation systems more successively, completes hydrocracking stage, obtains light-weight fuel oil;
Wherein, the described No. 1 each bed of guard reactor and catalyst loading ratio are: the metal remover of the first bed filling 60V%, the ZDL-T1 agent of the second bed filling 20V%, the ZDL-T2 agent of the 3rd bed filling 20V%;
The described No. 2 each beds of refining reaction device and catalyst loading ratio are: the ZDL-J1 agent of the first bed filling 20V%, the second bed filling ZDL-J1 agent of 15V% and ZDL-J2 agent of 20V%, the ZDL-J2 agent of the 3rd bed filling 45V%;
The described No. 3 each beds of reforming reactor and catalyst loading ratio are: the ZDL-G1 agent of the first bed filling 25V%, the second bed filling ZDL-G1 agent of 15V% and ZDL-G2 agent of 25V%, the ZDL-G2 agent of the 3rd bed filling 35V%;
The described No. 4 each beds of refining reaction device and catalyst loading ratio are: the ZDL-J1 agent of the first bed filling 20V%, the second bed filling ZDL-J1 agent of 15V% and ZDL-J2 agent of 20V%, the ZDL-J2 agent of the 3rd bed filling 45V%;
The described No. 5 each beds of cracking case and catalyst loading ratio are: the ZDL-L1 agent of the first bed filling 25V%, the mixture of the second bed filling ZDL-L1 agent of 15V% and the ZDL-L2 agent of 10V%, the 3rd bed filling ZDL-L1 agent of 10V% and the ZDL-L2 agent of 15V%, the ZDL-L2 agent of the 4th bed filling 25V%.
In above-mentioned grading method of catalyst, the concrete composition of each catalyzer is as follows:
Described ZDL-T1 agent component is: with catalyst weight, and carrier MCM-41 mesopore molecular sieve accounts for 75%, active ingredient MoO
3account for 8%, auxiliary agent NiO, P
2o
5difference 10%, 7%; Its pore volume 1.0-1.2mL/g, specific surface area 140-160m
2/ g, bore dia is that 25-100nm, 30-50nm account for more than 80V%;
Described ZDL-T2 agent component is: with catalyst weight, carrier A l
2o
380% is accounted for, active ingredient MoO with MCM-41 mesopore molecular sieve
3account for 7%, auxiliary agent NiO, P
2o
5difference 8%, 5%; Its pore volume 1.0-1.2mL/g, specific surface area 140-160m
2/ g, bore dia is that 25-100nm, 20-40nm account for more than 80V%;
Described ZDL-J1 agent component is: with catalyst weight, the complex carrier that carrier is made up of titanium dioxide and aluminum oxide, and wherein titanium dioxide accounts for 5%, alumina catalyst support accounts for 65%, active ingredient MoO
3, WO
3account for 5%, 8% respectively, auxiliary agent NiO, P
2o
5, C
o2o
3, MgO, ruthenium salt accounts for 4%, 6.5%, 2%, 2.5%, 2% respectively; Its pore volume 0.5-0.7mL/g, specific surface area 165-175m
2/ g, bore dia is that 8-100nm, 20-40nm account for more than 80V%.
Described ZDL-J2 agent component is: with catalyst weight, the complex carrier that carrier is made up of titanium dioxide and aluminum oxide, and wherein titanium dioxide accounts for 4%, aluminum oxide accounts for 63%, active ingredient MoO
3, WO
3account for 5%, 5% respectively, auxiliary agent NiO, P
2o
5, C
o2o
3, MgO, ruthenium salt accounts for 6%, 6%, 3%, 4%, 4% respectively; Its pore volume 0.6-0.8mL/g, specific surface area 160-180m
2/ g, bore dia is that 9-100nm, 15-25nm account for more than 80V%.
Described ZDL-G1 agent component is: with catalyst weight, and alumina catalyst support accounts for 70%, Zn, Mg and aluminum oxide and reacts the carrier Zinc aluminate that generates spinel structure or magnesium aluminate accounts for 5%, active ingredient NiO, WO
3, MoO
3account for 6% respectively, 5%, 14%; Its pore volume 0.58-0.8mL/g, specific surface area 310-330m
2/ g, bore dia is that 8-100nm, 20-40nm account for more than 80V%.
Described ZDL-G2 agent component is: with catalyst weight, and alumina catalyst support accounts for 63%, Zn, Mg and aluminum oxide and reacts the carrier Zinc aluminate or magnesium aluminate 7%, active ingredient NiO, WO that generate spinel structure
3, MoO
3account for 5% respectively, 5%, 20%; Its pore volume 0.62-0.9mL/g, specific surface area 300-330m2/g, bore dia is that 7-100nm, 15-25nm account for more than 80V%.
Described ZDL-L1 agent component is: with catalyst weight, alumina catalyst support account for 61% and silicon-dioxide account for 4%, Zn, Mg and aluminum oxide and react the carrier Zinc aluminate or magnesium aluminate 5%, active ingredient WO that generate spinel structure
3, MoO
3account for 3%, 12% respectively, auxiliary agent NiO account for 8%, C
o2o
3account for 7%; Its pore volume 0.61-0.9mL/g, specific surface area 330-350m
2/ g, bore dia is that 8-100nm, 20-40nm account for more than 80V%.
Described ZDL-L2 agent component is: with catalyst weight, alumina catalyst support accounts for 65%, and silicon-dioxide accounts for 6%, Zn, Mg and aluminum oxide and reacts the Zinc aluminate or magnesium aluminate 8%, active ingredient WO that generate spinel structure
3, MoO
3account for 8%, 5% respectively, auxiliary agent NiO account for 4%, C
o2o
3account for 4%; Its pore volume 0.57-0.7mL/g, specific surface area 320-330m
2/ g, bore dia is that 6-100nm, 15-25nm account for more than 80V%.
For coordinating above-mentioned catalyzer grading distribution scheme, its hydrogenation technique reaction conditions is:
Hydrofinishing state: pressure is 13.6MPa, hydrogen to oil volume ratio 1200:1 (V/V); No. 1 guard reactor temperature in 250 DEG C, exports 281 DEG C, cumulative volume air speed 1.25h
-1; No. 2 refining reaction device temperature ins 300 DEG C, temperature out 369 DEG C, cumulative volume air speed 0.88h
-1; No. 3 reforming reactor temperature ins 330 DEG C, temperature out 386 DEG C, cumulative volume air speed 0.81h
-1;
Hydrocracking stage: pressure is 16.8MPa, hydrogen to oil volume ratio 1600:1 (V/V); No. 4 refining reaction device temperature ins 330 DEG C, temperature out 381 DEG C, cumulative volume air speed 0.35h
-1; No. 5 cracking case temperature ins 370 DEG C, temperature out 386 DEG C, cumulative volume air speed 1.42h
-1.
Experimental example 2
According to the method loading catalyst of embodiment 1, difference is:
The described No. 1 each bed of guard reactor and catalyst loading ratio are: the metal remover of the first bed filling 55V%, the ZDL-T1 agent of the second bed filling 25V%, the ZDL-T2 agent of the 3rd bed filling 20V%;
The described No. 2 each beds of refining reaction device and catalyst loading ratio are: the ZDL-J1 agent of the first bed filling 18V%, the second bed filling ZDL-J1 agent of 17V% and ZDL-J2 agent of 19V%, the ZDL-J2 agent of the 3rd bed filling 46V%;
The described No. 3 each beds of reforming reactor and catalyst loading ratio are: the ZDL-G1 agent of the first bed filling 22V%, the second bed filling ZDL-G1 agent of 19V% and ZDL-G2 agent of 23V%, the ZDL-G2 agent of the 3rd bed filling 36V%;
The described No. 4 each beds of refining reaction device and catalyst loading ratio are: the ZDL-J1 agent of the first bed filling 15V%, the second bed filling ZDL-J1 agent of 19V% and ZDL-J2 agent of 21V%, the ZDL-J2 agent of the 3rd bed filling 45V%;
The described No. 5 each beds of cracking case and catalyst loading ratio are: the ZDL-L1 agent of the first bed filling 22V%, the mixture of the second bed filling ZDL-L1 agent of 19V% and the ZDL-L2 agent of 10V%, the 3rd bed filling ZDL-L1 agent of 13V% and the ZDL-L2 agent of 12V%, the ZDL-L2 agent of the 4th bed filling 24V%.
For coordinating above-mentioned catalyzer grading distribution scheme, its hydrogenation technique reaction conditions is:
Hydrofinishing state: pressure is 13.6MPa, hydrogen to oil volume ratio 1500:1 (V/V); No. 1 guard reactor temperature in 260 DEG C, exports 275 DEG C, cumulative volume air speed 1.28h
-1; No. 2 refining reaction device temperature ins 310 DEG C, temperature out 372 DEG C, cumulative volume air speed 0.85h
-1; No. 3 reforming reactor temperature ins 350 DEG C, temperature out 380 DEG C, cumulative volume air speed 0.85h
-1;
Hydrocracking stage: pressure is 17.5MPa, hydrogen to oil volume ratio 2000:1 (V/V); No. 4 refining reaction device temperature ins 340 DEG C, temperature out 370 DEG C, cumulative volume air speed 0.45h
-1; No. 5 cracking case temperature ins 372 DEG C, temperature out 390 DEG C, cumulative volume air speed 1.35h
-1.
Experimental example 3
According to the method loading catalyst of embodiment 1, difference is:
The described No. 1 each bed of guard reactor and catalyst loading ratio are: the metal remover of the first bed filling 65V%, the ZDL-T1 agent of the second bed filling 20V%, the ZDL-T2 agent of the 3rd bed filling 15V%;
The described No. 2 each beds of refining reaction device and catalyst loading ratio are: the ZDL-J1 agent of the first bed filling 15V%, the second bed filling ZDL-J1 agent of 20V% and ZDL-J2 agent of 21V%, the ZDL-J2 agent of the 3rd bed filling 44V%;
The described No. 3 each beds of reforming reactor and catalyst loading ratio are: the ZDL-G1 agent of the first bed filling 20V%, the second bed filling ZDL-G1 agent of 21V% and ZDL-G2 agent of 18V%, the ZDL-G2 agent of the 3rd bed filling 41V%;
The described No. 4 each beds of refining reaction device and catalyst loading ratio are: the ZDL-J1 agent of the first bed filling 20V%, the second bed filling ZDL-J1 agent of 18V% and ZDL-J2 agent of 23V%, the ZDL-J2 agent of the 3rd bed filling 39V%;
The described No. 5 each beds of cracking case and catalyst loading ratio are: the ZDL-L1 agent of the first bed filling 25V%, the mixture of the second bed filling ZDL-L1 agent of 20V% and the ZDL-L2 agent of 12V%, the 3rd bed filling ZDL-L1 agent of 10V% and the ZDL-L2 agent of 15V%, the ZDL-L2 agent of the 4th bed filling 18V%.
For coordinating above-mentioned catalyzer grading distribution scheme, its hydrogenation technique reaction conditions is:
Hydrofinishing state: pressure is 13.6MPa, hydrogen to oil volume ratio 1500:1 (V/V); No. 1 guard reactor temperature in 260 DEG C, exports 275 DEG C, cumulative volume air speed 1.28h
-1; No. 2 refining reaction device temperature ins 310 DEG C, temperature out 372 DEG C, cumulative volume air speed 0.85h
-1; No. 3 reforming reactor temperature ins 350 DEG C, temperature out 380 DEG C, cumulative volume air speed 0.85h
-1;
Hydrocracking stage: pressure is 17.5MPa, hydrogen to oil volume ratio 2000:1 (V/V); No. 4 refining reaction device temperature ins 340 DEG C, temperature out 370 DEG C, cumulative volume air speed 0.45h
-1; No. 5 cracking case temperature ins 372 DEG C, temperature out 390 DEG C, cumulative volume air speed 1.35h
-1.
Compliance test result is tested
Product checking: after running 6000h by adopting the hydrogenation unit of catalyzer grating described in embodiment 1-3, products obtained therefrom carries out Indexs measure,
The results are shown in Table 2.Analytical procedure comprises GB/T 1884-1885, SH/T0689, SH/T0704, GB/T386.
Table 2
As seen from table, after adopting catalyzer grading distribution scheme of the present invention, products obtained therefrom cetane value, octane value are compared currently available products and are all significantly improved; The more existing catalyzer of catalyst life obviously extends simultaneously, thus reduces device quantity and maintenance load, reduces production cost.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (9)
1. grading method of catalyst in a coal tar hydrogenating process, it is characterized in that, hydrogenation technique is: enter No. 1 guard reactor, No. 2 refining reaction devices, No. 3 reforming reactors, height separation systems after stock oil mixes with hydrogen successively, complete hydrofinishing state; Liquid after separation enters fractionating system, and gained tail oil enters No. 4 refining reaction devices, No. 5 cracking cases, height separation systems more successively, completes hydrocracking stage, obtains light-weight fuel oil;
Wherein, each catalyst reactor grating is specific as follows:
The described No. 1 each bed of guard reactor and catalyst loading ratio are: the metal remover of the first bed filling 55-65V%, the ZDL-T1 agent of the second bed filling 20-25V%, the ZDL-T2 agent of the 3rd bed filling 15-20V%;
The described No. 2 each beds of refining reaction device and catalyst loading ratio are: the ZDL-J1 agent of the first bed filling 15-20V%, the second bed filling ZDL-J1 agent of 15-20V% and ZDL-J2 agent of 19-21V%, the ZDL-J2 agent of the 3rd bed filling 44-46V%;
The described No. 3 each beds of reforming reactor and catalyst loading ratio are: the ZDL-G1 agent of the first bed filling 20-25V%, the second bed filling ZDL-G1 agent of 15-21V% and ZDL-G2 agent of 18-25V%, the ZDL-G2 agent of the 3rd bed filling 35-41V%;
The described No. 4 each beds of refining reaction device and catalyst loading ratio are: the ZDL-J1 agent of the first bed filling 15-20V%, the second bed filling ZDL-J1 agent of 15-19V% and ZDL-J2 agent of 20-23V%, the ZDL-J2 agent of the 3rd bed filling 39-45V%;
The described No. 5 each beds of cracking case and catalyst loading ratio are: the ZDL-L1 agent of the first bed filling 22-25V%, the second bed filling ZDL-L1 agent of 15-20V% and the ZDL-L2 agent of 10-12V%, the 3rd bed filling ZDL-L1 agent of 10-13V% and the ZDL-L2 agent of 12-15V%, the ZDL-L2 agent of the 4th bed filling 18-25V%.
2. grading method of catalyst in coal tar hydrogenating process according to claim 1, it is characterized in that, the described No. 1 each bed of guard reactor and catalyst loading ratio are: the metal remover of the first bed filling 60V%, the ZDL-T1 agent of the second bed filling 20V%, the ZDL-T2 agent of the 3rd bed filling 20V%;
The described No. 2 each beds of refining reaction device and catalyst loading ratio are: the ZDL-J1 agent of the first bed filling 20V%, the second bed filling ZDL-J1 agent of 15V% and ZDL-J2 agent of 20V%, the ZDL-J2 agent of the 3rd bed filling 45V%;
The described No. 3 each beds of reforming reactor and catalyst loading ratio are: the ZDL-G1 agent of the first bed filling 25V%, the second bed filling ZDL-G1 agent of 15V% and ZDL-G2 agent of 25V%, the ZDL-G2 agent of the 3rd bed filling 35V%;
The described No. 4 each beds of refining reaction device and catalyst loading ratio are: the ZDL-J1 agent of the first bed filling 20V%, the second bed filling ZDL-J1 agent of 15V% and ZDL-J2 agent of 20V%, the ZDL-J2 agent of the 3rd bed filling 45V%;
The described No. 5 each beds of cracking case and catalyst loading ratio are: the ZDL-L1 agent of the first bed filling 25V%, the mixture of the second bed filling ZDL-L1 agent of 15V% and the ZDL-L2 agent of 10V%, the 3rd bed filling ZDL-L1 agent of 10V% and the ZDL-L2 agent of 15V%, the ZDL-L2 agent of the 4th bed filling 25V%.
3. grading method of catalyst in coal tar hydrogenating process according to claim 1 and 2, it is characterized in that, described ZDL-J1 agent component is: with catalyst weight, the complex carrier that carrier is made up of titanium dioxide and aluminum oxide, wherein titanium dioxide accounts for 3-5%, alumina catalyst support accounts for 60-67%, active ingredient MoO
3, WO
3account for 3-9%, 5-10% respectively, auxiliary agent NiO, P
2o
5, C
o2o
3, MgO, ruthenium salt accounts for 4-5%, 6.5-8%, 1-3%, 2-7%, 2-3% respectively; Its pore volume 0.5-0.7mL/g, specific surface area 165-175m
2/ g, bore dia is that 8-100nm, 20-40nm account for more than 80V%.
4. grading method of catalyst in coal tar hydrogenating process according to claim 1 and 2, it is characterized in that, described ZDL-J2 agent component is: with catalyst weight, the complex carrier that carrier is made up of titanium dioxide and aluminum oxide, wherein titanium dioxide accounts for 3-5%, aluminum oxide accounts for 62-65%, active ingredient MoO
3, WO
3account for 4-8%, 4-6% respectively, auxiliary agent NiO, P
2o
5, C
o2o
3, MgO, ruthenium salt accounts for 5-7%, 5-6%, 2-5%, 2-4%, 3-4% respectively; Its pore volume 0.6-0.8mL/g, specific surface area 160-180m
2/ g, bore dia is that 9-100nm, 15-25nm account for more than 80V%.
5. grading method of catalyst in coal tar hydrogenating process according to claim 1 and 2, is characterized in that, described ZDL-T1 agent component is: with catalyst weight, and carrier MCM-41 mesopore molecular sieve accounts for 70-80%, active ingredient MoO
3account for 7-9%, auxiliary agent NiO, P
2o
58-10%, 2-7% respectively; Its pore volume 1.0-1.2mL/g, specific surface area 140-160m
2/ g, bore dia is that 25-100nm, 30-50nm account for more than 80V%;
Described ZDL-T2 agent component is: with catalyst weight, carrier A l
2o
370-80% is accounted for, active ingredient MoO with MCM-41 mesopore molecular sieve
3account for 7-9%, auxiliary agent NiO, P
2o
58-10%, 2-7% respectively; Its pore volume 1.0-1.2mL/g, specific surface area 140-160m
2/ g, bore dia is that 25-100nm, 20-40nm account for more than 80V%.
6. grading method of catalyst in coal tar hydrogenating process according to claim 1 and 2, it is characterized in that, described ZDL-G1 agent component is: with catalyst weight, alumina catalyst support accounts for 65-75%, Zn, Mg and aluminum oxide react the carrier Zinc aluminate that generates spinel structure or magnesium aluminate accounts for 5-7%, active ingredient NiO, WO
3, MoO
3account for 5-8% respectively, 2-8%, 6-20%; Its pore volume 0.58-0.8mL/g, specific surface area 310-330m
2/ g, bore dia is that 8-100nm, 20-40nm account for more than 80V%;
Described ZDL-G2 agent component is: with catalyst weight, alumina catalyst support accounts for 60-65%, and Zn, Mg and aluminum oxide react the carrier Zinc aluminate that generates spinel structure or magnesium aluminate 6-8%, active ingredient NiO, WO
3, MoO
3account for 5-10% respectively, 5-8%, 17-22%; Its pore volume 0.62-0.9mL/g, specific surface area 300-330m2/g, bore dia is that 7-100nm, 15-25nm account for more than 80V%.
7. grading method of catalyst in coal tar hydrogenating process according to claim 1 and 2, it is characterized in that, described ZDL-L1 agent component is: with catalyst weight, alumina catalyst support accounts for 60-65% and silicon-dioxide accounts for 4-6%, Zn, Mg and aluminum oxide react the carrier Zinc aluminate or magnesium aluminate 5-7%, active ingredient WO that generate spinel structure
3, MoO
3account for 3-5%, 6-15% respectively, auxiliary agent NiO accounts for 8-10%, C
o2o
3account for 7-9%; Its pore volume 0.61-0.9mL/g, specific surface area 330-350m
2/ g, bore dia is that 8-100nm, 20-40nm account for more than 80V%;
Described ZDL-L2 agent component is: with catalyst weight, alumina catalyst support accounts for 60-65%, and silicon-dioxide accounts for 6-8%, and Zn, Mg and aluminum oxide react the Zinc aluminate or magnesium aluminate 8-10%, active ingredient WO that generate spinel structure
3, MoO
3account for 8-10%, 5-15% respectively, auxiliary agent NiO accounts for 3-5%, C
o2o
3account for 3-5%; Its pore volume 0.57-0.7mL/g, specific surface area 320-330m2/g, bore dia is that 6-100nm, 15-25nm account for more than 80V%.
8. according to grading method of catalyst in the arbitrary described coal tar hydrogenating process of claim 1-7; it is characterized in that; hydrofinishing state: pressure is 8-15MPa; hydrogen to oil volume ratio 800-1800:1 (V/V); No. 1 guard reactor temperature of reaction is 230-280 DEG C, cumulative volume air speed 1.2-1.3h
-1, No. 2 refining reaction device temperature of reaction are 330-380 DEG C, cumulative volume air speed 0.8-0.9h
-1, No. 3 reforming reactor temperature of reaction are 360-390 DEG C, cumulative volume air speed 0.8-0.9h
-1.
9. according to grading method of catalyst in the arbitrary described coal tar hydrogenating process of claim 1-7, it is characterized in that, hydrocracking stage: pressure is 15-19MPa, hydrogen to oil volume ratio 1500-2800:1 (V/V), No. 4 refining reaction device temperature of reaction are 330-380 DEG C, cumulative volume air speed 0.3-1.1h
-1, No. 5 cracking case temperature of reaction are 370-390 DEG C, cumulative volume air speed 1.0-1.5h
-1.
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| CN107434982A (en) * | 2016-05-27 | 2017-12-05 | 神华集团有限责任公司 | The method and the hydrogenation method for upgrading of coal tar that device and catalyst grade for coal tar hydrogenating upgrading are matched somebody with somebody |
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|---|---|---|---|---|
| CN1903994A (en) * | 2006-08-03 | 2007-01-31 | 湖南长岭石化科技开发有限公司 | Method of producing fuel oil by coal tar hydrogenation modifying |
| CN101294107A (en) * | 2007-04-24 | 2008-10-29 | 中国石油化工股份有限公司 | Method for preparing fuel oil with coal oil hydrogenation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1903994A (en) * | 2006-08-03 | 2007-01-31 | 湖南长岭石化科技开发有限公司 | Method of producing fuel oil by coal tar hydrogenation modifying |
| CN101294107A (en) * | 2007-04-24 | 2008-10-29 | 中国石油化工股份有限公司 | Method for preparing fuel oil with coal oil hydrogenation |
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| CN107434982A (en) * | 2016-05-27 | 2017-12-05 | 神华集团有限责任公司 | The method and the hydrogenation method for upgrading of coal tar that device and catalyst grade for coal tar hydrogenating upgrading are matched somebody with somebody |
| CN107434982B (en) * | 2016-05-27 | 2019-05-03 | 神华集团有限责任公司 | Method that device and catalyst grade for coal tar hydrogenating upgrading are matched and coal tar plus hydrogen method for upgrading |
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