CN113336350B - Coal-to-hydrogen ash dehydration method and device without flocculating agent consumption - Google Patents

Coal-to-hydrogen ash dehydration method and device without flocculating agent consumption Download PDF

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CN113336350B
CN113336350B CN202110743759.9A CN202110743759A CN113336350B CN 113336350 B CN113336350 B CN 113336350B CN 202110743759 A CN202110743759 A CN 202110743759A CN 113336350 B CN113336350 B CN 113336350B
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ash
coal
gas
micro
bed
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CN113336350A (en
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刘毅
程婷婷
马凯
杨云峰
纪宗义
黄青松
汪华林
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East China University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Physical Water Treatments (AREA)

Abstract

The invention relates to a coal-to-hydrogen ash dehydration method and a device for canceling consumption of a flocculating agent, and provides the coal-to-hydrogen ash dehydration method for canceling consumption of the flocculating agent, which comprises the following steps: (i) Micro-channels are adopted to separate and treat coal hydrogen production ash slag so as to realize the solid removal of coal hydrogen production wastewater; (ii) Periodically adopting high-temperature gas to blow off, regenerate and dry the micro-channel filtration medium bed layer so as to avoid ash from permeating downwards along the bed layer medium and ensure that the gas carries the dried ash to form ascending gas flow so as to be separated from micro-channel medium particles; and (iii) realizing high-temperature gas purification and dried ash recycling by using gas-solid cyclone separation, wherein purified gas is circularly blown off. Also provides a coal-to-hydrogen ash dehydration device which can eliminate the consumption of flocculation reagents.

Description

Coal-to-hydrogen ash dehydration method and device without flocculating agent consumption
Technical Field
The disclosure belongs to the field of coal water slurry hydrogen production, and relates to a harmless low-cost treatment method and a device for coal hydrogen wastewater with ash residue wastewater solidification and drying ash residue recovery, in particular to a pretreatment method for coal hydrogen wastewater with fluidized bed separation and cyclone separation coupling, and a fully-closed device for implementing the method.
Background
At present, the demand of hydrogen as clean energy and chemical raw materials with extremely large consumption in the field of petrochemical industry is still very huge, and a large amount of ash waste water is generated in the process of producing hydrogen from petroleum coke, mainly because partial coal ash is discharged along with water due to insufficient combustion process and the waste water containing ash cannot be directly introduced into a biochemical pool. At present, for coal hydrogen production wastewater, domestic refineries generally adopt a combined process of pretreatment, biochemical treatment and advanced treatment. The pretreatment process mainly removes ash in water, is the throat of a complete set of sewage treatment process, and the key of ash waste water treatment lies in efficiently removing the ash in water and realizing the recycling of the ash.
At present, the ubiquitous problems of the pretreatment device for wastewater from hydrogen production by coal water slurry in refineries are as follows: the flow of the pretreatment process is long, the treatment equipment is a structure, and the occupied area is large. The traditional gravity settling, flocculation and filtration methods are low in separation efficiency and high in separation cost, ash in waste water can be effectively recovered by using a mode of combining physical settling and agent flocculation, but the problems that the agent consumption is too large, the treatment cost is too high, the facility occupies a large area, so that the tank body is complex to clean, the solid content separation does not reach the standard, the operation environment is bad and the like exist.
Aiming at high-content ash in coal-to-hydrogen wastewater, the mainstream direction for optimizing the ash wastewater pretreatment process is to integrate and replace dosing flocculation and long-time sedimentation in the existing ash wastewater pretreatment process through equipment, and the common treatment method is a method of medicament sedimentation, vacuum filtration and the like.
In order to solve the problem of high-concentration ash in the incoming water, CN108821406A provides a method and a process for adding a medicament twice in sequence to remove the ash in the coal-to-hydrogen wastewater, and according to the current method for removing suspended matters through electrocoagulation, the power consumption is high, the reinforced coagulation is easily influenced by external factors, the process route can better utilize the medicament to precipitate the ash in the wastewater at normal temperature and normal pressure, but the consumption of the medicament is excessive, and the moisture content of the ash removed by the precipitated medicament is high.
CN110482738A proposes a method for removing most ash in coal gasification wastewater by firstly adjusting pH and then precipitating aeration separation, and the treatment device adopts an integrated structure, and does not need to add a flocculating agent in the whole removing process. However, the subsequent nursing and maintenance cost of the waste alkali liquor input pipeline of the pH adjusting area and the construction investment cost of the precipitation device are high.
CN206109116U adopts the principle of electrochemical flocculation, removes the lime-ash in the coal gasification waste water high-efficiently through the electric flocculation reactor in the electrochemical reaction district that sets up, need not to add flocculating agent and dispersant, and is high to the treatment effeciency of containing the waste water of high lime-ash, has solved the problem that coal gasification waste water emission is big and system scale deposit, but adopts the electrochemical method mainly to have the defects such as electrode passivation and electrolytic polarization, power consumption is big, running cost height.
In addition, CN211367185U is for preventing the scale deposit of coal gasifier's water circulating line from blockking up, and lime-ash waste water filters the suspended solid through filter equipment earlier, gets rid of the hard ion in the waste water through adsorption equipment again, and the low suspended solid, the circulating water of low rigidity has strengthened coal gasifier's operational safety, but to the processing of the regeneration waste liquid that activates hard ion adsorption equipment, has increased treatment cost, occupation of land and the flow is complicated.
The existing coal gasification wastewater treatment process is continuously and deeply researched on an ash slag wastewater harmless treatment method, but the existing method still has certain defects on pursuit of industrialization and economy, and the existing research processes all have the problems of substandard indexes in sewage, low ash slag separation efficiency and high separation cost. In addition, the existing research is less aiming at the aspect of efficiently removing ash slag with low cost in the coal gasification wastewater treatment.
Therefore, in view of the above-mentioned drawbacks of the prior art, there is a need in the art to develop a method and an apparatus for efficiently pre-treating ash waste water, which can overcome the above-mentioned drawbacks of the prior art.
Disclosure of Invention
The present disclosure provides a novel coal-derived hydrogen ash dehydration method and apparatus without flocculation agent consumption, thereby overcoming the defects in the prior art.
In one aspect, the present disclosure provides a coal-to-hydrogen ash dehydration method without consumption of a flocculation reagent, comprising the steps of:
(i) Micro-channels are adopted to separate and treat coal hydrogen production ash slag so as to realize the solid removal of coal hydrogen production wastewater;
(ii) Periodically adopting high-temperature gas to blow off, regenerate and dry the micro-channel filtration medium bed layer so as to avoid ash from permeating downwards along the bed layer medium and ensure that the gas carries the dried ash to form an ascending gas flow so as to be separated from micro-channel medium particles; and
(iii) High-temperature gas purification and dried ash recovery are realized by gas-solid cyclone separation, and purified gas is blown off circularly.
In a preferred embodiment, in step (i), the effluent is subjected to the solid removal by using a boiling bed separator, and after the effluent is subjected to the solid removal, the suspended substance of the coal-to-hydrogen ash at the outlet of the boiling bed separator is not more than 150mg/L.
In another preferred embodiment, in step (ii), the blowing off, regeneration and drying are carried out by using a blowing device, and the air volume of the carrier gas per unit mass of the ash filter cake is 0.5-2m 3 /kg。
In another preferred embodiment, in step (ii), the temperature of the high-temperature gas is 60 to 180 ℃.
In another preferred embodiment, in the step (ii), after the bed media is backwashed, regenerated and dried by using high-temperature gas, the annual loss rate of the bed media is not more than 20%; the backwashing frequency is 8-24 h/time.
In another preferred embodiment, in step (iii), the moisture content of the ash after drying separation is <40%.
In another preferred embodiment, the ratio of residual ash to initial ash in the bed medium does not exceed 1.
In another aspect, the present disclosure provides a coal-to-hydrogen ash dewatering device that cancels consumption of a flocculating agent, the device comprising:
the fluidized bed separator is used for performing step (i) and separating and treating coal hydrogen production ash slag by adopting a micro-channel so as to realize the solid removal of coal hydrogen production wastewater;
the blowing equipment is connected with the boiling bed separator and is used for carrying out step (ii) and periodically adopting high-temperature gas to blow off, regenerate and dry the micro-channel filtration medium bed layer so as to avoid ash from permeating downwards along the bed layer medium and ensure that the gas carries the dried ash to form an ascending gas flow so as to be separated from micro-channel medium particles; and
and (5) a cyclone separator connected with the boiling bed separator and used for performing step (iii) and realizing high-temperature gas purification and dried ash recovery by using gas-solid cyclone separation, wherein purified gas is circularly blown off.
In a preferred embodiment, the apparatus further comprises a buffer tank connected to the ebullated bed separator for preliminary mixing of the coal-to-liquid hydrogen ash.
In another preferred embodiment, the cyclonic separator takes the form of an external housing; the bed layer filler of the fluidized bed separator is quartz sand with the grain diameter of 0.5-1 mm; the throughput of the device is 0.8-1.2m 3 H, 0.8m of floor area 2 (ii) a The operating pressure drop of the boiling bed separator is not higher than 0.10MPa, and the back flushing pressure drop is not higher than 10KPa.
Has the advantages that:
1) The ash dehydration process of the method of the invention cancels the consumption of flocculating agent, and has good ash purification effect and sufficient ash dehydration.
2) The device ensures low-cost dehydration and drying of the POX ash and discharge of purified ash water.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification to further illustrate the disclosure and not limit the disclosure.
Fig. 1 is a schematic process flow diagram of ash dehydration treatment of coal-to-hydrogen wastewater according to a preferred embodiment of the present disclosure.
Fig. 2 is a schematic view of a coal-to-hydrogen wastewater pretreatment process flow according to a preferred embodiment of the present disclosure.
Detailed Description
The inventor of the application develops a high-efficiency pretreatment method and a device suitable for ash and slag wastewater by aiming at the problems in the prior art, namely, zero consumption of equipment prototypes and chemical reagents and high-efficiency removal of ash and slag in wastewater by a physical method as an entry point through extensive and intensive research, utilizes mechanical separation and filtration and cyclone drying to realize pretreatment of drying and ash discharge, completely adopts the physical method, and ensures that the solid content of the pretreated ash and slag sewage effluent is less than 150mg/L and reaches the national standard.
In a first aspect of the present disclosure, there is provided a coal-to-hydro ash dehydration method with elimination of consumption of a flocculation reagent, the method comprising the steps of:
(i) POX ash slag with high water content is separated and treated by adopting a micro-channel so as to realize the solid removal of the coal-based hydrogen gasification wastewater;
(ii) Periodically adopting high-temperature gas to blow off, regenerate and dry the micro-channel filtration medium bed layer so as to avoid ash from permeating downwards along the bed layer medium and ensure that the gas carries the dried ash to form ascending gas flow so as to be separated from micro-channel medium particles; and
(iii) High-temperature gas purification and dried ash recovery are realized by gas-solid cyclone separation, and purified gas is blown off circularly.
In the disclosure, in step (i), the effluent is subjected to solid removal by using an ebullated bed separator, and POX ash water suspended matter at the outlet of the ebullated bed separator is not more than 150mg/L after ash in a coal hydrogen production device is subjected to solid removal by the effluent.
In the present disclosure, in step (ii), the stripping, regeneration and drying are carried out using an air blowing device, and the air volume of the carrier gas per unit mass of the filter cake is 0.5 to 2m 3 /kg。
In the present disclosure, in step (ii), the temperature of the high-temperature gas during the back flushing of the ebullated-bed separator is 60-180 ℃.
In the present disclosure, in step (ii), the bed media of the ebullated bed separator is backwashed, regenerated and dried by the high-temperature gas, and the annual loss rate of the bed media is not more than 20%.
In the present disclosure, in the step (ii), the back washing frequency of the treatment engineering device is 8-24 h/time for ash in the coal hydrogen production device.
In the present disclosure, in step (ii), the moisture content of the ash after drying separation is less than 40%.
In the present disclosure, the ratio of residual ash to initial ash in the bed medium does not exceed 1.
In a second aspect of the present disclosure, there is provided a coal-to-hydro ash dewatering device that cancels consumption of a flocculating agent, the device comprising:
a buffer tank for primarily mixing the water-coal-slurry hydrogen production wastewater;
the air blowing device is connected with the buffer tank and is used for blowing off, regenerating and drying the micro-channel filtration medium bed layer;
the fluidized bed separator is connected with the blast equipment and is used for removing solid particles and suspended matters in the ash-slag wastewater; and
and the cyclone separator is connected with the boiling bed separator and is used for realizing separation of ash and bed filter materials and recovery of dried ash.
In the present disclosure, the cyclone separator for separating the fluidized bed separator cut off filter ash takes the form of an external one.
In the disclosure, the bed packing of the fluidized bed separator is quartz sand with the grain diameter of 0.5-1 mm.
In the disclosure, the treatment capacity of the high-efficiency coal-to-hydrogen ash and slag wastewater removal device is 0.8-1.2m 3 H, 0.8m of floor area 2 。
In the present disclosure, the ebullated-bed separator operating pressure drop is no greater than 0.10MPa.
In the present disclosure, the ebullated bed separator backwash pressure drop is no greater than 10KPa.
Reference is made to the accompanying drawings.
Fig. 1 is a schematic process flow diagram of ash dehydration treatment of coal-to-hydrogen wastewater according to a preferred embodiment of the present disclosure. As shown in figure 1, the incoming water of the water-coal-slurry hydrogen production wastewater enters a boiling bed separator 3 to remove solid particles and suspended matters in ash-slag wastewater; meanwhile, blowing hot air into the fluidized bed separator 3 by using a blowing device so as to blow off, regenerate and dry the micro-channel filtration medium bed layer; the dried ash separated by the boiling bed separator 3 enters a cyclone separator 4 to separate the ash from the bed filter material and recover POX ash.
Fig. 2 is a schematic flow diagram of a coal-to-hydrogen wastewater pretreatment process according to a preferred embodiment of the present disclosure. As shown in fig. 2, the coal-to-hydrogen wastewater first enters a buffer tank 1 for preliminary mixing, and then enters a boiling bed separator 3 for removing solid particles and suspended matters in the wastewater; meanwhile, blowing hot air into the fluidized bed separator 3 by the blowing device 2 to blow off, regenerate and dry the micro-channel filtration medium bed layer; the dried ash separated by the boiling bed separator 3 enters a cyclone separator 4 to separate the ash from the bed filter material, and the dried ash is recovered.
Examples
The invention is further illustrated below with reference to specific examples. It is to be understood, however, that these examples are illustrative only and are not to be construed to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the manufacturer. All percentages and parts are by weight unless otherwise indicated.
Example 1:
this embodiment is applied to in the wastewater pretreatment system is produced in the preparation of hydrogen of Zhehai refining coal slurry, and the mode that the current wastewater pretreatment in this base adopted medicament to subside + vacuum filtration, and the consumption of medicament is too big, and the processing cost is high and there are the clear mud of cell body loaded down with trivial details and the facility takes up an area of too big, removes the not up to standard scheduling problem admittedly. The method is adopted for treatment, and the treatment process flow is shown in figure 2.
1. Key equipment
The key equipment in the process flow is a boiling bed separator and a cyclone separator, wherein the equipment treatment capacity is 0.7m in the experimental process 3 H is used as the reference value. In practical application, different numbers of devices can be selected to be connected in parallel according to different processing capacities. In the embodiment, only one boiling bed separator device is selected for separate experiments.
2. Process parameters
In the embodiment, the flow rate of the ash-containing waste water entering the boiling bed separator is 0.7m 3 H, the operating pressure drop is not higher than 0.10MPa, and the operating temperature is 40-90 ℃.
3. Operational effects
The device for micro-channel oscillation separation is adopted to continuously carry out experiments on water coming from the tank field, and the solid content of the inlet water is as follows: 10000mg/L and the solid content of the effluent is 0.3mg/L.
In the embodiment, the complete process flow is short, the device has a simple structure, the fluidized bed separation equipment completely adopting a physical method cancels the consumption of a focusing flocculating agent in the conventional process, the filtration of ash and slag in wastewater is realized by depending on a micro-channel filtration medium bed layer, the operation cost is low, high-temperature gas is introduced to periodically blow off, regenerate and dry a medium filter material, and the ash water purification effect is good. In addition, the cyclone separator can effectively realize the recovery of the dried ash and the moisture content of the ash is lower than 40 percent.
The device-sealed pretreatment process of the boiling bed separator has the characteristics of high solid removal efficiency, complete sealing, elimination of consumption of flocculating agents and the like from the viewpoints of equipment improvement and process idea adjustment, and the pretreatment method has stable ash removal effect, can remove most suspended matters in the grey water, and can meet the requirement of the water quality of inlet water of a subsequent advanced treatment unit.
The above-listed embodiments are merely preferred embodiments of the present disclosure, and are not intended to limit the scope of the present disclosure. That is, all equivalent changes and modifications made according to the contents of the claims of the present application should be considered to be within the technical scope of the present disclosure.
All documents referred to in this disclosure are incorporated by reference into this application as if each were individually incorporated by reference. Further, it should be understood that various changes or modifications to the present disclosure may be made by those skilled in the art after reading the above teachings of the present disclosure, and such equivalents are also within the scope of the appended claims.

Claims (7)

1. A coal-to-hydrogen ash dehydration method without flocculating agent consumption comprises the following steps:
(i) The coal-made hydrogen production ash is separated and treated by adopting a micro-channel to realize the solid removal of the coal-made hydrogen gasification wastewater, wherein a boiling bed separator is used for removing the solid of the wastewater, and the suspended substance of the coal-made hydrogen ash at the outlet of the boiling bed separator is not more than 150mg/L after the wastewater is removed;
(ii) Periodically adopting high-temperature gas to blow off, regenerate and dry the micro-channel filtration medium bed layer so as to avoid ash from permeating downwards along the bed layer medium and ensure that the gas carries the dried ash to form an ascending gas flow so as to be separated from micro-channel medium particles, wherein the carrier gas air quantity of the ash filter cake per unit mass is 0.5-2 m/kg, and the annual loss rate of the bed layer medium is not more than 20% after the bed layer medium is backwashed, regenerated and dried by adopting the high-temperature gas; the backwashing frequency is 8-24 h/time; and
(iii) High-temperature gas purification and dried ash recovery are realized by gas-solid cyclone separation, purified gas is circularly blown off, wherein gas-solid cyclone separation is carried out by using a cyclone separator which is externally arranged, and the moisture content of the dried and separated ash is less than 40%.
2. The method of claim 1, wherein in step (ii), the stripping, regenerating and drying are performed using a blower device.
3. The method of claim 1, wherein in step (ii), the temperature of the hot gas is 60-180 ℃.
4. The process of claim 1 wherein the ratio of residual ash to initial ash in the bed medium does not exceed 1.
5. A coal-to-hydro ash dewatering device for the process of claim 1 that eliminates the consumption of flocculating agents, the device comprising:
the boiling bed separator (3) is used for separating and treating coal-made hydrogen production ash slag by adopting a micro-channel in the step (i) so as to realize the solid removal of the coal-made hydrogen gasification wastewater;
the blowing device (2) is connected with the boiling bed separator (3) and is used for carrying out step (ii) and periodically adopting high-temperature gas to blow off, regenerate and dry the micro-channel filtration medium bed layer so as to avoid ash from permeating downwards along the bed layer medium and ensure that the gas carries the dried ash to form an ascending gas flow so as to be separated from micro-channel medium particles, wherein the carrier gas air volume of the ash filter cake per unit mass is 0.5-2 m/kg; and
and the cyclone separator (4) is connected with the boiling bed separator (3) and is used for performing step (iii) and realizing high-temperature gas purification and dried ash recovery by using gas-solid cyclone separation, and the purified gas is circularly blown off, wherein the cyclone separator (4) is externally arranged.
6. The apparatus according to claim 5, characterized by further comprising a buffer tank (1) connected to the ebullated bed separator (3) for preliminary mixing of the coal hydroash.
7. The device as claimed in claim 5 or 6, characterized in that the bed packing of the ebullated bed separator (3) is quartz sand with a particle size of 0.5-1 mm; the throughput of the device is 0.8-1.2m 3 /h, footprint is 0.8 m; the operating pressure drop of the boiling bed separator (3) is not higher than 0.10MPa, and the back flushing pressure drop is not higher than 10KPa.
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CN110093180A (en) * 2019-04-26 2019-08-06 河南百优福生物能源有限公司 A kind of biomass pyrolysis liquid ebullated bed outlet catalyst recovery process and device
CN112624472A (en) * 2020-12-17 2021-04-09 华东理工大学 Flash evaporation-sedimentation-ebullated bed separation combined coal gasification black water purification method and device
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