CN105087066A - Coal tar all-fraction liquid-phase hydrogenation system and method - Google Patents
Coal tar all-fraction liquid-phase hydrogenation system and method Download PDFInfo
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Abstract
The invention discloses a coal tar all-fraction liquid-phase hydrogenation system and method. The system comprises a liquid-phase reactor and a hydrogen dissolver, wherein an inlet of the hydrogen dissolver is connected with a coal tar pretreatment device and a hydrogen conveyor; an outlet of the hydrogen dissolver is connected to a lower end inlet of liquid-phase reactor; a reaction generation product outlet on the top end of the liquid-phase reactor is connected with a hot high-pressure separator; one outlet of the hot high-pressure separator is connected with a lower end inlet of the liquid-phase reactor through a circulating pump; the liquid-phase reactor comprises a liquid-phase reactor wall, hydrogen supplementing devices and a plurality of catalyst bed layers; the plurality of catalyst bed layers are arranged inside the liquid-phase reactor from bottom to top; and each hydrogen supplementing device is arranged between every two adjacent catalyst bed layers and communicated with the hydrogen conveyor. The coal tar all-fraction liquid-phase hydrogenation system and method have the advantages of reasonable design, reliable technical process and stable safety performance, greatly enhance the inner space utilization ratio of the liquid-phase reactor, reduce the equipment investment, and effectively enhance the reaction product yield.
Description
Technical field
The invention belongs to coal tar hydrogenating field, be specifically related to a kind of full fraction of coal tar liquid-phase hydrogenatin system and method.
Background technology
During the nearly last ten years, the preparing fuel oil by coal tar hydrogenation technology of China has had and has developed rapidly, realize the technical matters of suitability for industrialized production mainly at present: coal tar lighting end hydrogenation, delay coking of coal tar-hydrogenation and full fraction of coal tar hydrogenation, although its technical matters is different, coal tar hydrogenating agent technology all adopts traditional trickle bed hydrogenation reaction technical matters.This technical matters all needs to adopt larger hydrogen to oil volume ratio in process of production, and after reaction, hydrogen rich gas is by after recycle compressor supercharging, common as the raw material reacted with the new hydrogen supplemented.Coal tar adopts trickle bed hydrogen addition technology technique, easily cause liquid phase coal tar and hydrogen mixing inequality, or there is channel at beds in liquid phase coal tar, and the partially wetting of local catalyst outside surface, and have impact on catalyst reaction performance significantly, and in trickle bed hydrogenator, easily cause catalyzer coking, caking, bed resistance to increase, cause catalyst life to shorten.Therefore there is the problems such as investment is high, energy consumption is high, catalyst use efficiency is low in coal tar trickle bed hydrogenation technique.
In patent CN102585899B, a kind of full liquid phase hydrogenating method of coal tar is described, but this technology has the following disadvantages:
(1) add solubility promoter according to the weight ratio 1:1 ~ 2:1 of coal tar and solvent oil, make hydrogenating materials, significantly can reduce the treatment capacity of hydrogenator to stock oil thus, add hydrogenation unit investment, reduce Technical Economy.
(2) adopting downflow reactor when actual production operates, in order to ensure that administration measure runs, and maintaining level stability, need complicated reactor inner member and instrument to control to realize.
(3) in technical process, be still provided with recycle compressor, not only fail to embody the advantage of liquid-phase hydrogenatin technique, and make its technological process be tending towards complicated, add facility investment.
In view of the foregoing, a kind of technical matters of reasonable in design, technological process is reliable, safety performance is stable coal tar liquid-phase hydrogenatin need be provided.
Summary of the invention
In order to solve the deficiency of prior art processes, the invention provides a kind of full fraction of coal tar liquid-phase hydrogenatin system and method.
The present invention is achieved through the following technical solutions:
A kind of full fraction of coal tar liquid-phase hydrogenatin system, comprises Liquid-phase reactor and hydrogen-dissolving device, the import of hydrogen-dissolving device is connected with coal tar pretreatment unit and hydrogen conveyor, hydrogen-dissolving device outlet is connected to the lower end ingress of Liquid-phase reactor, the reaction on Liquid-phase reactor top generates product exit and is connected with high pressure hot separator, an outlet of high pressure hot separator is connected with the import of Liquid-phase reactor lower end after recycle pump, Liquid-phase reactor comprises liquid phase reaction wall, mend hydrogen production device and multi-layer catalyst bed, Liquid-phase reactor pars intramuralis is from bottom to top provided with multi-layer catalyst bed, benefit hydrogen production device is provided with between every two adjacent beds, mend hydrogen production device to be connected with hydrogen conveyor.
Lower bed layer, middle bed and upper bed layer three layers of beds are from bottom to top housed in described liquid phase reaction wall; benefit hydrogen production device is provided with between lower bed layer and middle bed; benefit hydrogen production device is provided with between middle bed and upper bed layer; wherein; lower bed layer is filled with hydrogenation protecting agent; middle bed is filled with hydro-upgrading agent, and upper bed layer is filled with hydrocracking agent.
Described coal tar pretreatment unit comprises refining plant, High pressure feeding pump and process furnace, and described refining plant import has passed into coal tar, and refining plant outlet is connected with process furnace through High pressure feeding pump, and process furnace is connected with hydrogen-dissolving device import.
Described hydrogen conveyor comprises hydrogen gas compressor, and hydrogen gas compressor is connected with hydrogen-dissolving device import.
Described benefit hydrogen production device comprises dissolved-air head and the benefit hydrogen pipe with hydrogen inlet, mending hydrogen pipe racks has one end of hydrogen inlet to be arranged on liquid phase reaction wall, the other end extend in Liquid-phase reactor cavity, mend hydrogen pipe to be connected with hydrogen conveyor, mend on hydrogen pipe and be provided with the dissolved-air head communicated with it, be provided with catalyst support plate above dissolved-air head, above and below catalyst support plate, be equipped with beds.
Another outlet of described high pressure hot separator is connected with water distilling apparatus.
Described dissolved-air head comprises dish and lower wall, and upper dish and lower wall are fixed by tumbler pin, and forms the gap of 2 ~ 3mm, leaves air inlet port, be connected with inlet pipe below air inlet port by support bar in the middle of lower wall.
A kind of full fraction of coal tar liquid phase hydrogenating method, comprises the following steps:
1) will purify and be heated to 260 ~ 320 DEG C coal tar send into hydrogen-dissolving device, and the hydrogen after compression is sent in hydrogen-dissolving device, coal tar in hydrogen-dissolving device after heating and hydrogen, at 260 ~ 320 DEG C, under the condition of 11 ~ 16MPa, the molten hydrogen time is 5 ~ 15min, makes coal tar reach molten hydrogen state of saturation, becomes molten hydrogen coal tar;
2) passed into bottom Liquid-phase reactor by molten hydrogen coal tar, Liquid-phase reactor bottom inlet temperature is 260 ~ 320 DEG C, and pressure is 11 ~ 16MPa; Molten hydrogen coal tar is from bottom to top according to 0.28 ~ 2.5h
-1volume space velocity by each layer beds in Liquid-phase reactor, make the catalyzer of beds all be infiltrated by molten hydrogen coal tar and react uniformly, obtain reacting generation product;
3) reaction generate product by temperature be 350 ~ 420 DEG C, pressure be 10 ~ 14MPa Liquid-phase reactor top exit send into high pressure hot separator, by high pressure hot separator sidepiece, reaction is generated oil and send into rectifier unit, by ordinary method, cut out petroleum naphtha, diesel oil distillate and mink cell focus; By bottom high pressure hot separator, one partial reaction is generated oil as turning oil, mix send into Liquid-phase reactor after recycle pump supercharging with the molten hydrogen coal tar in step 1, wherein, the internal circulating load of turning oil is that reaction generates 20% ~ 55% of oily total amount.
Described step 1) further comprising the steps of before:
4) full fraction of coal tar adopts known method to process in refining plant, removes the moisture in coal tar, metal and solid impurity; After being pumped in process furnace being heated to 260 ~ 320 DEG C by high pressure charging by coal tar after purification, send into hydrogen-dissolving device, wherein, described coal tar is one in coalite tar, medium/low temperature coal tar and coal-tar middle oil or mixture;
5) hydrogen is sent in hydrogen-dissolving device after hydrogen gas compressor.
Step 3) also comprise: at high pressure hot separator upper end outlet, sent by dry gas, the treatment unit entering downstream routine is processed.
Described step 2) be specially:
Passed into bottom Liquid-phase reactor by molten hydrogen coal tar, Liquid-phase reactor bottom inlet temperature is 260 ~ 320 DEG C, and pressure is 11 ~ 16MPa; Molten hydrogen coal tar is from bottom to top according to 0.28 ~ 2.5h
-1the three layer beds of volume space velocity by loading in Liquid-phase reactor, and between upper bed layer and middle bed, all fill into hydrogen between middle bed and lower bed layer, make the catalyzer of beds all be infiltrated by molten hydrogen coal tar and react uniformly, obtain reaction and generate product; Wherein, described lower bed layer has loaded hydrogenation protecting agent; in Liquid-phase reactor bed, shared volume ratio is 20% ~ 30%; middle bed has loaded hydro-upgrading agent; in Liquid-phase reactor bed, shared volume ratio is 40% ~ 50%; upper bed layer has loaded hydrocracking agent, and in Liquid-phase reactor bed, shared volume ratio is 20% ~ 25%.
Compared with prior art, the present invention has following useful technique effect:
(1) in Liquid-phase reactor, the molten hydrogen coal tar of liquid phase reaction thing passes through beds from bottom to top, catalyzer can be made all to be infiltrated by reaction mass uniformly, catalyst action is not fully exerted, can effectively improve reaction product yield, the thermal capacitance of the molten hydrogen coal tar of liquid phase is comparatively large, and bed temperature can be made to be controlled effectively.
(2) beds of Liquid-phase reactor inside carries out layering setting, increases dissolved hydrogen on a catalyst and mend hydrogen production device between lower bed layer, and then the consumption of replenisher phased soln hydrogen.
(3) Liquid-phase reactor is adopted, eliminate refrigerating unit between the apparatus for redistributing between complicated entrance gas-liquid two-phase distribution apparatus and beds, beds, substantially increase the internal space utilization ratio of Liquid-phase reactor, decrease facility investment.
(4) arrange dissolved hydrogen between beds and mend hydrogen production device, it is strong that this device has dissolve hydrogen capacity, the feature that structure is simple, easy for installation.
Accompanying drawing explanation
Accompanying drawing 1 is the schematic diagram of a kind of full fraction of coal tar liquid-phase hydrogenatin system provided by the invention.In figure, sequence number 1 is refining plant, and 2 is High pressure feeding pump, and 3 is process furnace, and 4 is hydrogen-dissolving device, 5 is Liquid-phase reactor, and 6 is hydrogen gas compressor, and 7 is high pressure hot separator, 8 is recycle pump, and 9 is water distilling apparatus, and B-1 is lower bed layer, B-2 is middle bed, and B-3 is upper bed layer, and a is coal tar, b is hydrogen, and c is dry gas, and d is petroleum naphtha, e is diesel oil distillate, and f is mink cell focus, A and B is hydrogen make-up.
Accompanying drawing 2 is benefit hydrogen production device structural representations of the present invention.In figure, sequence number 11 is liquid phase reaction wall, and 12 and 15 is beds, and 13 is catalyst support plate, and 14 is dissolved-air head, and 16 is hydrogen inlet, and 17 for mending hydrogen pipe.
Accompanying drawing 3 is benefit hydrogen production device vertical views of the present invention.Sequence number 14 dissolved-air head in figure, 16 is hydrogen inlet, and 17 for mending hydrogen pipe.
Accompanying drawing 4 is dissolved-air head structural representations of the present invention.In figure, sequence number 14-1 is upper dish, and 14-2 is lower wall, and 14-3 is inlet pipe, and 14-4 is air inlet port, and 14-5 is tumbler pin.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, and the explanation of the invention is not limited.
See Fig. 1 to Fig. 4, a kind of full fraction of coal tar liquid-phase hydrogenatin system, comprises Liquid-phase reactor 5 and hydrogen-dissolving device 4, the import of hydrogen-dissolving device 4 is connected with coal tar pretreatment unit and hydrogen conveyor, hydrogen-dissolving device 4 outlet is connected to the lower end ingress of Liquid-phase reactor 5, the reaction on Liquid-phase reactor 5 top generates product exit and is connected with high pressure hot separator 7, an outlet of high pressure hot separator 7 is connected with Liquid-phase reactor 5 lower end import after recycle pump 8, Liquid-phase reactor 5 comprises liquid phase reaction wall 11, mend hydrogen production device and multi-layer catalyst bed, liquid phase reaction wall 11 inside is from bottom to top provided with multi-layer catalyst bed, benefit hydrogen production device is provided with between every two adjacent beds, mend hydrogen production device to be connected with hydrogen conveyor.
Wherein, lower bed layer B-1, middle bed B-2 and upper bed layer B-3 tri-layers of beds are from bottom to top housed in described liquid phase reaction wall 11; benefit hydrogen production device is provided with between lower bed layer B-1 and middle bed B-2; benefit hydrogen production device is provided with between middle bed B-2 and upper bed layer B-3; wherein; lower bed layer B-1 is filled with hydrogenation protecting agent, and middle bed B-2 is filled with hydro-upgrading agent, and upper bed layer B-3 is filled with hydrocracking agent.
Concrete, described coal tar pretreatment unit comprises refining plant 1, High pressure feeding pump 2 and process furnace 3, described refining plant 1 import has passed into coal tar, and refining plant 1 exports and is connected with process furnace 3 through High pressure feeding pump 2, and process furnace 3 is connected with hydrogen-dissolving device 4 import; Described hydrogen conveyor comprises hydrogen gas compressor 6, and hydrogen gas compressor 6 is connected with hydrogen-dissolving device 4 import.
Described benefit hydrogen production device comprises multiple dissolved-air head 14 and the benefit hydrogen pipe 17 with hydrogen inlet 16, benefit hydrogen pipe 17 is arranged on liquid phase reaction wall 11 with one end of hydrogen inlet 16, the other end extend in Liquid-phase reactor cavity, mend hydrogen pipe 17 to be connected with hydrogen conveyor, mend on hydrogen pipe 17 and be provided with the multiple dissolved-air heads 14 communicated with it, be provided with catalyst support plate 13 above dissolved-air head 14, above and below catalyst support plate 13, be equipped with beds 12,15.Benefit hydrogen production device between Liquid-phase reactor beds of the present invention have employed multiple dissolved-air head, the principle of work of dissolved-air head is the hydrogen by mending hydrogen pipe 17, carry out energy dissipating, dispersion, the hydrogen entering oil phase is made to become microbubble shape, and can mix with oil phase rapidly, there is good dissolve hydrogen capacity.
Described dissolved-air head 14 comprises dish 14-1 and lower wall 14-2, upper dish 14-1 and lower wall 14-2 is fixed by tumbler pin 14-5, and make to coil the gap forming 2 ~ 3mm between 14-1 and lower wall 14-2, leave air inlet port 14-4 in the middle of lower wall 14-2, below air inlet port 14-4, be connected with inlet pipe 14-3 by support bar.First hydrogen entered by inlet pipe, before lower wall air inlet port and inlet pipe, form jet action, and hydrogen is mixed with oil phase, enters the gap between upper dish and lower wall and flow out by air inlet port.
Further, another outlet of described high pressure hot separator 7 is connected with water distilling apparatus 9, described water distilling apparatus is provided with petroleum naphtha d, diesel oil distillate e and mink cell focus f and exports.
The burnt oil properties of feed coal is as shown in table 1.
Table 1 feed coal tar character
See Fig. 1 and table 1, a kind of full fraction of coal tar liquid phase hydrogenating method, comprises the following steps:
1) full fraction of coal tar adopts known method to process in refining plant, removes the moisture in coal tar a, metal and solid impurity; After being pumped in process furnace being heated to 260 ~ 320 DEG C by high pressure charging by coal tar after purification, send into hydrogen-dissolving device, wherein, described coal tar is one in coalite tar, medium/low temperature coal tar and coal-tar middle oil or mixture.
2) hydrogen b is sent in hydrogen-dissolving device after hydrogen gas compressor.
3) coal tar in hydrogen-dissolving device after heating and hydrogen, at 260 ~ 320 DEG C, under the condition of 11 ~ 16MPa, the molten hydrogen time is 5 ~ 15min, makes coal tar reach molten hydrogen state of saturation, becomes molten hydrogen coal tar;
4) passed into bottom Liquid-phase reactor by molten hydrogen coal tar, Liquid-phase reactor bottom inlet temperature is 260 ~ 320 DEG C, and pressure is 11 ~ 16MPa; Molten hydrogen coal tar is from bottom to top according to 0.28 ~ 2.5h
-1the three layer beds of volume space velocity by loading in Liquid-phase reactor, and between upper bed layer and middle bed, all fill into hydrogen between middle bed and lower bed layer, make the catalyzer of beds all be infiltrated by molten hydrogen coal tar and react uniformly, obtain reaction and generate product; Wherein, described lower bed layer has loaded hydrogenation protecting agent; in Liquid-phase reactor bed, shared volume ratio is 20% ~ 30%; middle bed has loaded hydro-upgrading agent; in Liquid-phase reactor bed, shared volume ratio is 40% ~ 50%; upper bed layer has loaded hydrocracking agent, and in Liquid-phase reactor bed, shared volume ratio is 20% ~ 25%.
Concrete, being from bottom to top filled with three layers of catalyzer in the Liquid-phase reactor in step, between upper bed layer B-3 and middle bed B-2, between middle bed B-2 and lower bed layer B-1, all filling into hydrogen A, B, for making up the consumption of liquid phase dissolved hydrogen.Wherein, described beds B-1 has loaded hydrogenation protecting agent, and (model is CH-13, Fushun Petrochemical Company oil three factory catalyst plant) in Liquid-phase reactor bed, shared volume ratio is 20% ~ 30%, beds B-2 has loaded hydro-upgrading agent, and (model is SSY-1A, Shaanxi Shui Senyin Energetix Group Ltd.) in Liquid-phase reactor bed, shared volume ratio is 40% ~ 50%, beds B-3 has loaded hydrocracking agent, and (model is SSY-21, Shaanxi Shui Senyin Energetix Group Ltd.) in Liquid-phase reactor bed, shared volume ratio is 20% ~ 25%.
5) reaction generate product by temperature be 350 ~ 420 DEG C, pressure be 10 ~ 14MPa Liquid-phase reactor top exit send into high pressure hot separator, at high pressure hot separator upper end outlet, dry gas is sent, the treatment unit entering downstream routine is processed, by high pressure hot separator sidepiece, reaction is generated oil and send into rectifier unit, by ordinary method, cut out petroleum naphtha, diesel oil distillate and mink cell focus; By bottom high pressure hot separator, one partial reaction is generated oil as turning oil, mix send into Liquid-phase reactor after recycle pump supercharging with the molten hydrogen coal tar in step 3, wherein, the internal circulating load of turning oil is that reaction generates 20% ~ 55% of oily total amount.
Embodiment 1
Take coalite tar as raw material, the method for full fraction of coal tar liquid-phase hydrogenatin system comprises the following steps:
Step 1: coalite tar a is removed moisture in refining plant 1, metal and solid impurity, the coal tar after being purified.
Step 2: the coal tar after purification sends into process furnace 3 by its heating temperatures to 280 DEG C by High pressure feeding pump 2.
Step 3: hydrogen b mixes in hydrogen-dissolving device 4 through the coal tar of hydrogen gas compressor 6 after heating, and molten hydrogen pressure is 13.5MPa, temperature is 280 DEG C, molten hydrogen time 10min, the molten hydrogen amount in coal tar is reached capacity state, becomes molten hydrogen coal tar.
Step 4: molten hydrogen coal tar is sent into by the bottom from Liquid-phase reactor 5, the inlet temperature of Liquid-phase reactor 5 is 273 DEG C, and pressure is 13MPa.Liquid-phase reactor 5 temperature out 380 DEG C, pressure are 12.1MPa.Liquid phase volume air speed 0.3h
-1.
Lower bed layer B-1 in Liquid-phase reactor 5 loads CH-13 type protective material, and in Liquid-phase reactor 5 bed, shared volume ratio is 25%; Middle bed B-2 loads the agent of SSY-1A type hydro-upgrading, and in Liquid-phase reactor 5 bed, shared volume ratio is 50%; Upper bed layer B-3 loads SSY-21 type hydrocracking agent, and in Liquid-phase reactor 5 bed, shared volume ratio is 25%.Between upper bed layer B-3 and middle bed B-2, inject hydrogen make-up A, between middle bed B-2 and lower bed layer B-1, inject hydrogen make-up B.
Step 5: the reaction in Liquid-phase reactor 5 generates product, send into high pressure hot separator 7 by the top exit of Liquid-phase reactor 5, sent by dry gas c at the upper end outlet of high pressure hot separator 7, the treatment unit entering downstream routine is processed.Exported by high pressure hot separator 7 lower end and sent by part reaction generation oil, send in Liquid-phase reactor 5 as turning oil through recycle pump 8, the internal circulating load of turning oil generates oily total amount 45% for reacting.By the sidepiece of high pressure hot separator 7, reaction is generated oil and send into rectifier unit 9.
Step 6: generation oil is sent into rectifier unit 9 and is separated, cut out petroleum naphtha d, diesel oil distillate e and mink cell focus f.
Generation petroleum naphtha and diesel oil distillate character are in table 2, table 3.
Embodiment 2
With medium/low temperature coal tar for raw material, the method for full fraction of coal tar liquid-phase hydrogenatin system comprises the following steps:
Step 1: medium/low temperature coal tar a is removed moisture, metal and solid impurity, the coal tar after being purified in refining plant 1.
Step 2: the coal tar after purification sends into process furnace 3 by its heating temperatures to 290 DEG C by High pressure feeding pump 2.
Step 3: hydrogen b mixes in hydrogen-dissolving device 4 through the coal tar of hydrogen gas compressor 6 after heating, and molten hydrogen pressure is 14MPa, temperature is 290 DEG C, molten hydrogen time 12min, the molten hydrogen amount in coal tar is reached capacity state, becomes molten hydrogen coal tar.
Step 4: molten hydrogen coal tar is sent into by the bottom from Liquid-phase reactor 5, the inlet temperature of Liquid-phase reactor 5 is 300 DEG C, and pressure is 12MPa.Liquid-phase reactor 5 temperature out 393 DEG C, pressure are 11.7MPa.Liquid phase volume air speed 0.42h
-1.
Lower bed layer B-1 in Liquid-phase reactor 5 loads CH-13 type protective material, and in Liquid-phase reactor 5 bed, shared volume ratio is 28%; Middle bed B-2 loads the agent of SSY-1A type hydro-upgrading, and in Liquid-phase reactor 5 bed, shared volume ratio is 48%; Upper bed layer B-3 loads SSY-21 type hydrocracking agent, and in Liquid-phase reactor 5 bed, shared volume ratio is 24%.Between upper bed layer B-3 and middle bed B-2, inject hydrogen make-up A, between middle bed B-2 and lower bed layer B-1, inject hydrogen make-up B.
Step 5: the reaction in Liquid-phase reactor 5 generates product, send into high pressure hot separator 7 by the top exit of Liquid-phase reactor 5, sent by dry gas c at the upper end outlet of high pressure hot separator 7, the treatment unit entering downstream routine is processed.Exported by high pressure hot separator 7 lower end and sent by part reaction generation oil, send in Liquid-phase reactor 5 as turning oil through recycle pump 8, the internal circulating load of turning oil generates oily total amount 37% for reacting.By the sidepiece of high pressure hot separator 7, reaction is generated oil and send into rectifier unit 9.
Step 6: generation oil is sent into rectifier unit 9 and is separated, cut out petroleum naphtha d, diesel oil distillate e and mink cell focus f.
Generation petroleum naphtha and diesel oil distillate character are in table 2, table 3.
Embodiment 3
Take coal-tar middle oil as raw material, the method for full fraction of coal tar liquid-phase hydrogenatin system comprises the following steps:
Step 1: coal-tar middle oil a is removed moisture in refining plant 1, metal and solid impurity, the coal tar after being purified.
Step 2: the coal tar after purification sends into process furnace 3 by its heating temperatures to 310 DEG C by High pressure feeding pump 2.
Step 3: hydrogen b mixes in hydrogen-dissolving device 4 through the coal tar of hydrogen gas compressor 6 after heating, and molten hydrogen pressure is 15MPa, temperature is 310 DEG C, molten hydrogen time 15min, the molten hydrogen amount in coal tar is reached capacity state, becomes molten hydrogen coal tar.
Step 4: molten hydrogen coal tar is sent into by the bottom from Liquid-phase reactor 5, the inlet temperature of Liquid-phase reactor 5 is 320 DEG C, and pressure is 15MPa.Liquid-phase reactor 5 temperature out 406 DEG C, pressure are 14MPa.Liquid phase volume air speed 0.65h
-1.
Lower bed layer B-1 in Liquid-phase reactor 5 loads CH-13 type protective material, and in Liquid-phase reactor 5 bed, shared volume ratio is 30%; Middle bed B-2 loads the agent of SSY-1A type hydro-upgrading, and in Liquid-phase reactor 5 bed, shared volume ratio is 49%; Upper bed layer B-3 loads SSY-21 type hydrocracking agent, and in Liquid-phase reactor 5 bed, shared volume ratio is 21%.Between upper bed layer B-3 and middle bed B-2, inject hydrogen make-up A, between middle bed B-2 and lower bed layer B-1, inject hydrogen make-up B.
Step 5: the reaction in Liquid-phase reactor 5 generates product, send into high pressure hot separator 7 by the top exit of Liquid-phase reactor 5, sent by dry gas c at the upper end outlet of high pressure hot separator 7, the treatment unit entering downstream routine is processed.Exported by high pressure hot separator 7 lower end and sent by part reaction generation oil, send in Liquid-phase reactor 5 as turning oil through recycle pump 8, the internal circulating load of turning oil generates oily total amount 45% for reacting.By the sidepiece of high pressure hot separator 7, reaction is generated oil and send into rectifier unit 9.
Step 6: generation oil is sent into rectifier unit 9 and is separated, cut out petroleum naphtha d, diesel oil distillate e and mink cell focus f.
Embodiment 4
Take coal-tar middle oil as raw material, the method for full fraction of coal tar liquid-phase hydrogenatin system comprises the following steps:
Step 1: coal-tar middle oil a is removed moisture in refining plant 1, metal and solid impurity, the coal tar after being purified.
Step 2: the coal tar after purification sends into process furnace 3 by its heating temperatures to 260 DEG C by High pressure feeding pump 2.
Step 3: hydrogen b mixes in hydrogen-dissolving device 4 through the coal tar of hydrogen gas compressor 6 after heating, and molten hydrogen pressure is 11MPa, temperature is 260 DEG C, molten hydrogen time 15min, the molten hydrogen amount in coal tar is reached capacity state, becomes molten hydrogen coal tar.
Step 4: molten hydrogen coal tar is sent into by the bottom from Liquid-phase reactor 5, the inlet temperature of Liquid-phase reactor 5 is 260 DEG C, and pressure is 11MPa.Liquid-phase reactor 5 temperature out 350 DEG C, pressure are 10MPa.Liquid phase volume air speed 2.5h
-1.
Lower bed layer B-1 in Liquid-phase reactor 5 loads CH-13 type protective material, and in Liquid-phase reactor 5 bed, shared volume ratio is 30%; Middle bed B-2 loads the agent of SSY-1A type hydro-upgrading, and in Liquid-phase reactor 5 bed, shared volume ratio is 50%; Upper bed layer B-3 loads SSY-21 type hydrocracking agent, and in Liquid-phase reactor 5 bed, shared volume ratio is 20%.Between upper bed layer B-3 and middle bed B-2, inject hydrogen make-up A, between middle bed B-2 and lower bed layer B-1, inject hydrogen make-up B.
Step 5: the reaction in Liquid-phase reactor 5 generates product, send into high pressure hot separator 7 by the top exit of Liquid-phase reactor 5, sent by dry gas c at the upper end outlet of high pressure hot separator 7, the treatment unit entering downstream routine is processed.Exported by high pressure hot separator 7 lower end and sent by part reaction generation oil, send in Liquid-phase reactor 5 as turning oil through recycle pump 8, the internal circulating load of turning oil generates oily total amount 45% for reacting.By the sidepiece of high pressure hot separator 7, reaction is generated oil and send into rectifier unit 9.
Step 6: generation oil is sent into rectifier unit 9 and is separated, cut out petroleum naphtha d, diesel oil distillate e and mink cell focus f.
Embodiment 5
Take coal-tar middle oil as raw material, the method for full fraction of coal tar liquid-phase hydrogenatin system comprises the following steps:
Step 1: coal-tar middle oil a is removed moisture in refining plant 1, metal and solid impurity, the coal tar after being purified.
Step 2: the coal tar after purification sends into process furnace 3 by its heating temperatures to 320 DEG C by High pressure feeding pump 2.
Step 3: hydrogen b mixes in hydrogen-dissolving device 4 through the coal tar of hydrogen gas compressor 6 after heating, and molten hydrogen pressure is 16MPa, temperature is 320 DEG C, molten hydrogen time 5min, the molten hydrogen amount in coal tar is reached capacity state, becomes molten hydrogen coal tar.
Step 4: molten hydrogen coal tar is sent into by the bottom from Liquid-phase reactor 5, the inlet temperature of Liquid-phase reactor 5 is 320 DEG C, and pressure is 16MPa.Liquid-phase reactor 5 temperature out 420 DEG C, pressure are 14MPa.Liquid phase volume air speed 0.28h
-1.
Lower bed layer B-1 in Liquid-phase reactor 5 loads CH-13 type protective material, and in Liquid-phase reactor 5 bed, shared volume ratio is 30%; Middle bed B-2 loads the agent of SSY-1A type hydro-upgrading, and in Liquid-phase reactor 5 bed, shared volume ratio is 49%; Upper bed layer B-3 loads SSY-21 type hydrocracking agent, and in Liquid-phase reactor 5 bed, shared volume ratio is 21%.Between upper bed layer B-3 and middle bed B-2, inject hydrogen make-up A, between middle bed B-2 and lower bed layer B-1, inject hydrogen make-up B.
Step 5: the reaction in Liquid-phase reactor 5 generates product, send into high pressure hot separator 7 by the top exit of Liquid-phase reactor 5, sent by dry gas c at the upper end outlet of high pressure hot separator 7, the treatment unit entering downstream routine is processed.Exported by high pressure hot separator 7 lower end and sent by part reaction generation oil, send in Liquid-phase reactor 5 as turning oil through recycle pump 8, the internal circulating load of turning oil generates oily total amount 45% for reacting.By the sidepiece of high pressure hot separator 7, reaction is generated oil and send into rectifier unit 9.
Step 6: generation oil is sent into rectifier unit 9 and is separated, cut out petroleum naphtha d, diesel oil distillate e and mink cell focus f.
It should be noted that, the full fraction of coal tar in above-described embodiment, be follow-uply called coal tar.
Generation petroleum naphtha and diesel oil distillate character are in table 2, table 3.
Table 2 petroleum naphtha character
Table 3 diesel oil distillate character
| Analysis project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Density (20 DEG C), kg/m 3 | 843 | 849 | 851 |
| Cetane value | 43 | 41 | 40 |
| Boiling range, DEG C | |||
| IBP/10％ | 128/173 | 130/189 | 143/192 |
| 50％ | 247 | 259 | 269 |
| 90％ | 323 | 333 | 342 |
| 95％ | 351 | 352 | 357 |
| FBP | 368 | 373 | 379 |
| Flash-point (remaining silent), DEG C | 42 | 40 | 45 |
| Viscosity (20 DEG C), mm 2/s | 3 | 4 | 5 |
| Condensation point, DEG C | -1 | -3 | -5 |
| Ash content, % | 0.0001 | 0.002 | 0.003 |
| 10% steams excess carbon residue, % | 0.18 | 0.21 | 0.23 |
| Total sulfur, ppm | 10 | 10 | 12 |
| Moisture, (v/v) | Vestige | Vestige | Vestige |
| Mechanical impurity | Nothing | Nothing | Nothing |
| Oxidation stability is always insoluble | 2.0 | 2.3 | 2.2 |
| Copper corrosion (50 DEG C, 3) level | ≯1 | ≯1 | ≯1 |
| Composition, % | |||
| Paraffinic hydrocarbons | 50.11 | 47.68 | 45.33 |
| Naphthenic hydrocarbon | 19.73 | 19.54 | 19.34 |
| Aromatic hydrocarbons | 21.32 | 22.53 | 25.77 |
| Alkene | 0.72 | 0.89 | 0.81 |
| Other | 8.12 | 9.36 | 8.75 |
The present invention adopts full fraction of coal tar liquid-phase hydrogenatin, liquid phase hydrogenation technology is dissolved in coal tar by the hydrogen needed for reaction in advance, there is provided required hydrogen source by the dissolved hydrogen in molten hydrogen coal tar for reaction, also there is the function of restraining coal tar resin and asphalt coking reaction simultaneously.Molten hydrogen coal tar enters beds together with the mixture of turning oil, and fluid is in the reactor in single liquid phase state.
The present invention has following characteristics:
(1) in Liquid-phase reactor, the molten hydrogen coal tar of liquid phase reaction thing passes through beds from bottom to top, catalyzer can be made all to be infiltrated by reaction mass uniformly, catalyst action is not fully exerted, can effectively improve reaction product yield, the thermal capacitance of the molten hydrogen coal tar of liquid phase is comparatively large, and bed temperature can be made to be controlled effectively.
(2) beds of Liquid-phase reactor inside carries out layering setting, increases dissolved hydrogen on a catalyst and mend hydrogen production device between lower bed layer, and then the consumption of replenisher phased soln hydrogen.
(3) Liquid-phase reactor is adopted, eliminate refrigerating unit between the apparatus for redistributing between complicated entrance gas-liquid two-phase distribution apparatus and beds, beds, substantially increase the internal space utilization ratio of Liquid-phase reactor, decrease facility investment.
(4) arrange dissolved hydrogen between beds and mend hydrogen production device, it is strong that this device has dissolve hydrogen capacity, the feature that structure is simple, easy for installation.
More than show and describe ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (10)
1. a full fraction of coal tar liquid-phase hydrogenatin system, is characterized in that, comprises Liquid-phase reactor (5) and hydrogen-dissolving device (4), the import of hydrogen-dissolving device (4) is connected with coal tar pretreatment unit and hydrogen conveyor, hydrogen-dissolving device (4) outlet is connected to the lower end ingress of Liquid-phase reactor (5), the reaction on Liquid-phase reactor (5) top generates product exit and is connected with high pressure hot separator (7), an outlet of high pressure hot separator (7) is connected with Liquid-phase reactor (5) lower end import after recycle pump (8), Liquid-phase reactor (5) comprises liquid phase reaction wall (11), mend hydrogen production device and multi-layer catalyst bed, liquid phase reaction wall (11) inside is from bottom to top provided with multi-layer catalyst bed, benefit hydrogen production device is provided with between every two adjacent beds, mend hydrogen production device to be connected with hydrogen conveyor.
2. full fraction of coal tar liquid-phase hydrogenatin system according to claim 1, it is characterized in that, in described liquid phase reaction wall (11), lower bed layer (B-1) is from bottom to top housed, middle bed (B-2) and upper bed layer (B-3) three layers of beds, benefit hydrogen production device is provided with between lower bed layer (B-1) and middle bed (B-2), benefit hydrogen production device is provided with between middle bed (B-2) and upper bed layer (B-3), wherein, lower bed layer (B-1) is filled with hydrogenation protecting agent, middle bed (B-2) is filled with hydro-upgrading agent, upper bed layer (B-3) is filled with hydrocracking agent.
3. full fraction of coal tar liquid-phase hydrogenatin system according to claim 1, it is characterized in that, described coal tar pretreatment unit comprises refining plant (1), High pressure feeding pump (2) and process furnace (3), described refining plant (1) import has passed into coal tar, refining plant (1) outlet is connected with process furnace (3) through High pressure feeding pump (2), and process furnace (3) is connected with hydrogen-dissolving device (4) import.
4. full fraction of coal tar liquid-phase hydrogenatin system according to claim 1, is characterized in that, described hydrogen conveyor comprises hydrogen gas compressor (6), and hydrogen gas compressor (6) is connected with hydrogen-dissolving device (4) import.
5. full fraction of coal tar liquid-phase hydrogenatin system according to claim 1, it is characterized in that, described benefit hydrogen production device comprises dissolved-air head (14) and the benefit hydrogen pipe (17) with hydrogen inlet (16), benefit hydrogen pipe (17) is arranged on liquid phase reaction wall (11) with one end of hydrogen inlet (16), the other end extend in Liquid-phase reactor cavity, mend hydrogen pipe (17) to be connected with hydrogen conveyor, mend on hydrogen pipe (17) and be provided with the multiple dissolved-air heads (14) communicated with it, dissolved-air head (14) top is provided with catalyst support plate (13), catalyst support plate is equipped with beds above and below (13).
6. full fraction of coal tar liquid-phase hydrogenatin system according to claim 5, it is characterized in that, described dissolved-air head (14) comprises dish (14-1) and lower wall (14-2), upper dish (14-1) and lower wall (14-2) are fixed by tumbler pin (14-5), and form the gap of 2 ~ 3mm, leave air inlet port (14-4) in the middle of lower wall (14-2), air inlet port (14-4) below is connected with inlet pipe (14-3) by support bar.
7. full fraction of coal tar liquid-phase hydrogenatin system according to claim 1, is characterized in that, another outlet of described high pressure hot separator (7) is connected with water distilling apparatus (9).
8., based on a full fraction of coal tar liquid phase hydrogenating method for the system described in claim 1 to 7, it is characterized in that, comprise the following steps:
1) will purify and be heated to 260 ~ 320 DEG C coal tar send into hydrogen-dissolving device, and the hydrogen after compression is sent in hydrogen-dissolving device, coal tar in hydrogen-dissolving device after heating and hydrogen, at 260 ~ 320 DEG C, under the condition of 11 ~ 16MPa, the molten hydrogen time is 5 ~ 15min, makes coal tar reach molten hydrogen state of saturation, becomes molten hydrogen coal tar;
2) passed into bottom Liquid-phase reactor by molten hydrogen coal tar, Liquid-phase reactor bottom inlet temperature is 260 ~ 320 DEG C, and pressure is 11 ~ 16MPa; Molten hydrogen coal tar is from bottom to top according to 0.28 ~ 2.5h
-1volume space velocity by each layer beds in Liquid-phase reactor, make the catalyzer of beds all be infiltrated by molten hydrogen coal tar and react uniformly, obtain reacting generation product;
3) reaction generate product by temperature be 350 ~ 420 DEG C, pressure be 10 ~ 14MPa Liquid-phase reactor top exit send into high pressure hot separator, by high pressure hot separator sidepiece, reaction is generated oil and send into rectifier unit, by ordinary method, cut out petroleum naphtha, diesel oil distillate and mink cell focus; By bottom high pressure hot separator, one partial reaction is generated oil as turning oil, mix send into Liquid-phase reactor after recycle pump supercharging with the molten hydrogen coal tar in step 1, wherein, the internal circulating load of turning oil is that reaction generates 20% ~ 55% of oily total amount.
9. full fraction of coal tar liquid phase hydrogenating method according to claim 8, is characterized in that, described step 1) further comprising the steps of before:
4) full fraction of coal tar adopts known method to process in refining plant, removes the moisture in coal tar, metal and solid impurity; After being pumped in process furnace being heated to 260 ~ 320 DEG C by high pressure charging by coal tar after purification, send into hydrogen-dissolving device, wherein, described coal tar is one in coalite tar, medium/low temperature coal tar and coal-tar middle oil or mixture;
5) hydrogen is sent in hydrogen-dissolving device after hydrogen gas compressor.
Step 3) also comprise: at high pressure hot separator upper end outlet, sent by dry gas, the treatment unit entering downstream routine is processed.
10. full fraction of coal tar liquid phase hydrogenating method according to claim 8, is characterized in that, described step 2) be specially:
Passed into bottom Liquid-phase reactor by molten hydrogen coal tar, Liquid-phase reactor bottom inlet temperature is 260 ~ 320 DEG C, and pressure is 11 ~ 16MPa; Molten hydrogen coal tar is from bottom to top according to 0.28 ~ 2.5h
-1the three layer beds of volume space velocity by loading in Liquid-phase reactor, and between upper bed layer and middle bed, all fill into hydrogen between middle bed and lower bed layer, make the catalyzer of beds all be infiltrated by molten hydrogen coal tar and react uniformly, obtain reaction and generate product; Wherein, described lower bed layer has loaded hydrogenation protecting agent; in Liquid-phase reactor bed, shared volume ratio is 20% ~ 30%; middle bed has loaded hydro-upgrading agent; in Liquid-phase reactor bed, shared volume ratio is 40% ~ 50%; upper bed layer has loaded hydrocracking agent, and in Liquid-phase reactor bed, shared volume ratio is 20% ~ 25%.
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