CN109233908A - A kind of coal catalytic hydrogenation gasification process and device - Google Patents
A kind of coal catalytic hydrogenation gasification process and device Download PDFInfo
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- CN109233908A CN109233908A CN201811103308.3A CN201811103308A CN109233908A CN 109233908 A CN109233908 A CN 109233908A CN 201811103308 A CN201811103308 A CN 201811103308A CN 109233908 A CN109233908 A CN 109233908A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/82—Gas withdrawal means
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Abstract
The present invention discloses a kind of coal catalytic hydrogenation gasification process and device, is related to Coal Gasification Technology field, invents to reduce coal hydrogenation gasification process costs.The coal catalytic hydrogenation gasification process includes: coal dust pretreatment: by coal dust, the first catalyst and sulphur, or mix coal dust, the first catalyst and sulfide, coal dust intermixture is made, wherein, first catalyst is transition metal halide, contains moisture in coal dust；Catalytic hydrogenation gasification: carrying out catalytic hydrogenation gasification for coal dust intermixture obtained, the gaseous mixture containing synthesis gas and oil product, the residue containing semicoke and the second catalyst is made；In catalytic hydrogenation gasification, the first catalyst is reacted with hydrogen generates transition metal, and transition metal is reacted with sulphur or sulfide again generates the second catalyst, and the second catalyst is transient metal sulfide.Coal catalytic hydrogenation gasification process and device of the present invention are for reducing process costs on the basis of ensureing efficiency of carbon con version, product yield.
Description
Technical field
The present invention relates to Coal Gasification Technology field more particularly to a kind of coal catalytic hydrogenation gasification process and device.
Background technique
The gasification of coal catalytic hydrogenation is coal dust and hydrogen to be occurred in certain temperature and pressure, and under the catalytic action of catalyst
Synthetic reaction is to generate synthesis gas, oil product and the process of semicoke, wherein for catalyst in synthetic reaction process, catalyst can be with
Redox reaction occurs for hydrogen, is elemental metals by catalyst reduction, and then can reduce the content of catalyst, reduces turning for carbon
Rate.For the efficiency of carbon con version for improving the gasification of coal catalytic hydrogenation, the mode for increasing catalyst is generallyd use, reaction rate is improved, adds
The deep extent of reaction reduces char yeild, improves efficiency of carbon con version and synthesis gas and oil product yield.But if by directly increasing valence
The mode of the catalyst of lattice valuableness reaches above-mentioned purpose, can increase accordingly process costs, is catalyzed particularly with larger coal
Hydrogasification technique, cost can obviously increase.
Summary of the invention
The embodiment provides a kind of coal catalytic hydrogenation gasification process and device, main purpose is to reduce coal catalysis
Hydrogasification process costs.
In order to achieve the above objectives, the embodiment of the present invention adopts the following technical scheme that
A kind of coal catalytic hydrogenation gasification process, comprising:
Coal dust pretreatment: mixing by coal dust, the first catalyst and sulphur, or by coal dust, the first catalyst and sulfide, with
Coal dust intermixture is made, wherein first catalyst is transition metal halide, contains moisture in the coal dust；
Catalytic hydrogenation gasification: the coal dust intermixture obtained is subjected to catalytic hydrogenation gasification, contains synthesis gas to be made
With the gaseous mixture of oil product, the residue containing semicoke and the second catalyst；Wherein, in catalytic hydrogenation gasification, described first
Catalyst is reacted with hydrogen generates transition metal, and the transition metal reacts the second catalysis of generation with the sulphur or sulfide again
Agent, second catalyst are transient metal sulfide.
Coal catalytic hydrogenation gasification process provided in an embodiment of the present invention, since sulphur or sulfide, coal being added in coal dust
In catalytic hydrogenation gasification synthetic reaction process, when the first catalyst generates the mistake without catalytic action under the reduction of hydrogen
When crossing metal simple-substance, sulphur or sulfide can react with transition metal and generate the second catalyst with catalytic action, this
Sample can make coal during entire hydrogasification, ensure the content of catalyst, meanwhile, it can also increase the content of reactive hydrogen, promote
Into hydrogasification reaction efficiency, improve the yield of charcoal percent conversion and product, compared to it is existing by increase expensive catalyst come
Ensure reaction efficiency, hence it is evident that process costs are reduced, and the coal catalytic hydrogenation gasification process is simple, it is practical.
Optionally, the pretreated detailed process of the coal dust are as follows:
Coal dust, halogen gas, transistion metal compound and sulphur are mixed, or by coal dust, halogen gas, transition metal
Close object and sulfide mixing, wherein the halogen gas and water reaction generate hydrogen halides, and the hydrogen halides is golden with the transition again
Belong to compound reaction and generates the first catalyst, first catalyst, the coal dust and the sulphur or first catalysis
Agent, the coal dust and the sulfide are mixed to get coal dust intermixture.
Further, after the catalytic hydrogenation gasification further include:
Residue pickling: will be obtained described containing the progress pickling of the residue of semicoke and the second catalyst, transition gold is made
Belong to halide solution and hydrogen sulfide；
The electrolysis of transition metal halide solution: will transition metal halide solution electrolysis obtained, be made hydrogen with
Halogen gas, wherein the halogen gas in the coal dust pretreatment is the halogen that the transition metal halide solution is electrolysed
Plain gas.
Further, in the transition metal halide solution electrolytic process: the transition metal halide solution
Concentration is more than or equal to 80%.
Optionally, in the residue acid cleaning process, using oxygen-free acid as pickling solution.
Optionally, in the residue acid cleaning process, the concentration of the pickling solution used is 10%~15%.
Optionally, after the catalytic hydrogenation gasification further include:
Gas-liquid refrigerated separation: by it is obtained it is described contain the gaseous mixture of synthesis gas and oil product carry out gas-liquid separation；
Desulfurization process: isolated synthesis gas is subjected to desulfurization process, and the sulphur that desulfurization process is obtained or vulcanization
At least partly sulphur or sulfide in object are returned in the coal dust pretreatment.
Optionally, after the catalytic hydrogenation gasification further include:
Gaseous mixture heat exchange: hydrogen and the catalytic hydrogenation gasification gaseous mixture obtained are subjected to heat exchange, then will be changed
Hydrogen after heat is returned in the catalytic hydrogenation gasification.
Optionally, in the catalytic hydrogenation gasification: the vapor pressure of catalytic hydrogenation gasification is 10~
30MPa, gasification temperature are 1000~1100 DEG C.
Another aspect of the present invention embodiment additionally provides a kind of coal catalytic hydrogenation gasification installation, comprising: storage sulphur device；Coal dust
Pretreatment unit, the feed inlet of the coal dust pretreatment unit are connected to the discharge port of the storage sulphur device, and the coal dust is located in advance
Reason device, which is matched, to be combined into coal dust, the first catalyst and sulphur, or coal dust, the first catalyst and sulfide are mixed；
Catalytic hydrogenation gasification reactor, the feed inlet of the catalytic hydrogenation gasification reactor and the coal dust pretreatment unit
Discharge port connection.
Coal catalytic hydrogenation gasification installation provided in an embodiment of the present invention, mixes coal dust using coal dust pretreatment unit
Processing, the catalytic hydrogenation gasification reactor being connected to the coal dust pretreatment unit can react inside it when specifically used
The second catalyst is generated, the content of catalyst is improved, and then ensure hydrogasification reaction efficiency, improves charcoal percent conversion and production
The yield of object.
Detailed description of the invention
Fig. 1 is a kind of flow diagram of coal catalytic hydrogenation gasification process provided in an embodiment of the present invention；
Fig. 2 is the flow diagram of another coal catalytic hydrogenation gasification process provided in an embodiment of the present invention；
Fig. 3 is the flow diagram of another coal catalytic hydrogenation gasification process provided in an embodiment of the present invention；
Fig. 4 is a kind of composition schematic diagram of coal catalytic hydrogenation gasification installation provided in an embodiment of the present invention.
Specific embodiment
Coal catalytic hydrogenation gasification process of the embodiment of the present invention and coal catalytic hydrogenation gasification installation are carried out with reference to the accompanying drawing
Detailed description.
In the description of the present invention, it is to be understood that, term " center ", "upper", "lower", "front", "rear", " left side ",
The orientation or positional relationship of the instructions such as " right side ", "vertical", "horizontal", "top", "bottom", "inner", "outside" is based on the figure
Orientation or positional relationship is merely for convenience of description of the present invention and simplification of the description, rather than the device of indication or suggestion meaning or
Element must have a particular orientation, be constructed and operated in a specific orientation, therefore be not considered as limiting the invention.
Term " first ", " second " be used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance or
Implicitly indicate the quantity of indicated technical characteristic." first " is defined as a result, the feature of " second " can be expressed or imply
Ground includes one or more of the features.In the description of the present invention, unless otherwise indicated, the meaning of " plurality " is two or
It is more than two.
The embodiment of the invention provides a kind of coal catalytic hydrogenation gasification process, referring to Fig.1, coal catalytic hydrogenation gasification side
The step of method includes:
S1: it coal dust pretreatment: is mixed by coal dust, the first catalyst and sulphur, or by coal dust, the first catalyst and sulfide
It closes, coal dust intermixture is made, wherein first catalyst is transition metal halide, contains moisture in the coal dust.
Specifically, the coal dust refers to that coal particle of the partial size less than or equal to 75 μm accounts for 90% of gross mass or more coal.Using
When the coal dust of the partial size carries out catalytic hydrogenation gasification reaction, the contact area of coal dust and catalyst can be increased, and then promote coal
The hydrogasification of powder is reacted.
Exemplary, first catalyst can be iron chloride (FeCl3), calcium chloride (CaCl2), copper chloride (CuCl2)、
Zinc bromide (ZnBr2) one of or multiple combinations, be also possible to other transition metal halides.
In some embodiments, in order to make full use of waste material, exhaust gas or the extra material in chemical producing system,
It carries out in coal dust pretreatment, first catalyst can be generated in whole or in part by following embodiments, specific mistake
Journey are as follows: mix coal dust, halogen gas, transistion metal compound and sulfide, wherein the halogen gas and water reaction generate
Hydrogen halides, the hydrogen halides is reacted with the transistion metal compound again generates the first catalyst.It is exemplary, the transition metal
Compound can be iron oxide (Fe2O3), lime stone (CaCO3), copper oxide (CuO), one of zinc oxide (ZnO) or a variety of
Combination, is also possible to other transistion metal compounds.The attainable technical effect of institute in this way are as follows: when halogen gas is passed through coal dust
Afterwards, halogen gas can loose coal dust, increase the contact area of coal dust and final obtained first catalyst, make coal dust with
First catalyst is uniformly mixed, it is ensured that the first catalyst plays maximum catalytic effect；By coal dust, halogen gas, transition metal
Compound and sulphur, or coal dust, halogen gas, transistion metal compound and sulfide are mixed together, it can also simplify technique step
Suddenly, simplify equipment.
S2: catalytic hydrogenation gasification: the coal dust intermixture obtained is subjected to catalytic hydrogenation gasification, to be made containing synthesis
The gaseous mixture of gas and oil product, the residue containing semicoke and the second catalyst；Wherein, in catalytic hydrogenation gasification, described
One catalyst is reacted with hydrogen generates transition metal, and the transition metal reacts generation second with the sulphur or sulfide again and urges
Agent, second catalyst are transient metal sulfide.
In specific hydrogasification synthetic reaction, the coal dust and hydrogen issue coal dust in the catalytic action of the first catalyst
GCMS computer reaction, generates synthesis gas, oil and semicoke, and the first catalyst occurs redox reaction and generate under the reduction of hydrogen
Transition metal, transition metal can be reacted with sulfide generates transient metal sulfide, and the transient metal sulfide is as second
Catalyst continues the synthetic reaction for being catalyzed coal dust and hydrogen, and the second catalyst for reacting generation continues catalytic hydrogenation reaction, ensures
Reaction efficiency, the yield of charcoal percent conversion, synthesis gas and oil.Compared to catalyst is directly increased, entire technique can effectively reduce
Cost, and take full advantage of the transition metal after the first catalyst is reduced.
First catalyst when redox reaction generation transition metal occurs, can also generate activity under the reduction of hydrogen
Hydrogen, increases the concentration of reactive hydrogen, and then promotes coal dust synthetic reaction, improves the yield of synthesis gas and oil, meanwhile, transition metal with
The transient metal sulfide that sulphur or sulfide reaction generate, can catalysed curing hydrogen decompose, generate reactive hydrogen, further increase work
The concentration of property hydrogen.
In specific reaction, reaction temperature can reach 1000 DEG C or more, so synthesis gas and oil product exist with gas phase, semicoke
Exist with the second catalyst with solid phase, can reach efficiently separating for the gaseous mixture of the second catalyst and synthesis gas and oil in this way,
On the basis of ensureing reaction efficiency, the separation of the second catalyst is realized, can reduce process flow in this way, reduce production cycle and system
Cause this.
After semicoke and the second catalyst are discharged, in order to utilize second catalyst again, referring to Fig. 2, the catalysis
After hydrogasification further include:
S3: residue pickling: will be obtained described containing the progress pickling of the residue of semicoke and the second catalyst, transition is made
Metal halide solution and hydrogen sulfide.
It is exemplary, in the residue acid cleaning process, can using oxygen-free acid as pickling solution, for example, HCl solution,
HBr solution, HF solution etc..Exemplary again, the concentration of the pickling solution used is 10%~15%, after can guarantee pickling in this way
The saturation degree of transition metal halide solution to ensure the electrolysis effectiveness of transition metal halide solution, and can also reduce sewage
Yield.
S4: the electrolysis of transition metal halide solution: the transition metal halide solution obtained is electrolysed, hydrogen is made
And halogen gas, wherein the halogen gas transition metal halide solution in the coal dust pretreatment is electrolysed to obtain
Halogen gas.
Specifically, being electrolysed to the transition metal halide solution, so that it may hydrogen and halogen gas be made, will be made
Halogen gas be passed through in the coal dust, as the raw material for preparing first catalyst, realize recycling for material, drop
Low entire process costs, meanwhile, hydrogen obtained is alternatively arranged as the gasifying agent of coal dust catalytic hydrogenation gasification reaction, is being embodied
When, the first catalyst quality if desired is larger, and is electrolysed halogen gas quality obtained and is unable to satisfy technique requirement, can also be with
Corresponding halogen gas is supplemented, it similarly, can also be to hydrogen if hydrogen quality made from being electrolysed also is unable to satisfy technique requirement
Gas carries out corresponding supplement.
Exemplary, the concentration of the transition metal halide solution is more than or equal to 80%, can accelerate the efficiency of electrolysis in this way,
Improve the production rate of hydrogen and halogen gas.
In order to reduce the energy consumption of catalytic hydrogenation gasification, referring to Fig. 3, after the catalytic hydrogenation gasification further include:
S5: gaseous mixture heat exchange: hydrogen and the catalytic hydrogenation gasification gaseous mixture obtained are subjected to heat exchange, then will
Hydrogen after heat exchange is returned in the catalytic hydrogenation gasification.Specifically, after the gasification of coal dust catalytic hydrogenation in gaseous mixture obtained
Containing biggish heat, in order to make full use of the heat, the energy consumption of gasifying agent in the gasification of coal catalytic hydrogenation is reduced, by hydrogen and institute
It states gaseous mixture and carries out heat exchange, then the hydrogen of the high temperature after heat exchange is returned in the catalytic hydrogenation gasification, wherein the hydrogen
Gas bag includes the hydrogen that transition metal halide solution is electrolysed, and sometimes further includes the hydrogen of supplement.
In some embodiments, referring to Fig. 3, after the catalytic hydrogenation gasification further include:
S6: gas-liquid refrigerated separation: by it is obtained it is described contain the gaseous mixture of synthesis gas and oil product carry out gas-liquid separation.Pass through
Gas-liquid refrigerated separation, so that it may obtain liquid phase oil, vapor- phase synthesis gas, wherein be mingled with sulphur-containing substance in vapor- phase synthesis gas, in order to fill
Divide using the sulphur or sulfide obtained after the gasification of coal dust catalytic hydrogenation, is urged using sulphur or sulfide as preparing described second
The raw material of agent, after step S6 further include: S7: desulfurization process: isolated synthesis gas being carried out desulfurization process, will be taken off
At least partly sulphur or sulfide that sulphuring treatment obtains in sulphur or sulfide are returned in the coal dust pretreatment, to be used to
Prepare the second catalyst.
It is following that the disclosure is described in detail by four examples.
Example one
Carry out the electrolysis of ferric chloride solution, wherein the concentration of ferric chloride solution preferably 80%~saturation, cell reaction formula is such as
Under:
2FeCl3+6H2O=2Fe (OH)3↓+3Cl2↑+3H2↑
The room temperature hydrogen that electrolysis obtains is mixed with the hydrogen (magnitude of recruitment is determined according to catalytic hydrogenation reaction needs) of supplement,
And heat is carried out with high temperature (for example, the 1000-1100 DEG C) gaseous mixture of the synthesis gas and oil product that are escaped by catalytic hydrogenation gasification reaction
Hydrogen is preheating to certain temperature (for example, 700-800 DEG C) into catalytic hydrogenation gasification reaction by exchange.It is electrolysed the hydrogen obtained,
Solves a part of hydrogen source of catalytic hydrogenation gasification.
The chlorine that electrolytic chlorination ferrous solution obtains pre-processes into coal dust, absorbs moisture entrained by a part of coal dust, and
With scrap iron powder (Fe2O3) reaction generates the first catalyst, i.e. ferric chloride catalyst, meanwhile, the loose coal dust of the introducing of chlorine makes
The ferric chloride catalyst that must be generated is uniformly mixed to a certain extent with coal dust, to ensure that ferric chloride catalyst plays maximum urge
Change effect.Wherein, the specific generating process of ferric chloride catalyst are as follows:
Cl2+H2O=HCl+HClO
6HCl+Fe2O3=2FeCl3+3H2O
Into the hydrogen of catalytic hydrogenation gasification reaction, a part generates enough heats with oxygen combustion, by remaining hydrogen, coal
The temperature of powder and the first catalyst mixture is increased to 1000-1100 DEG C, and catalytic hydrogenation gasification reaction is promoted to carry out, and generates synthesis
The high-temperature gas mixture of gas and oil product and solid residue containing the second catalyst.
Wherein, in the catalytic hydrogenation gasification reaction of high temperature and pressure (1000~1100 DEG C, 10~30MPa), iron chloride is urged
While changing hydrogasification reaction, by hydrogen reducing at fe, fe generates ferrous sulfide (FeS) with sulfur reaction again,
Ferrous sulfide (FeS) is the second catalyst, further promotes the progress of catalytic hydrogenation gasification reaction.Main catalyzed side reaction journey
Formula is as follows:
S+H2=H2S (generates reactive hydrogen)
2FeCl3+H2S=2FeCl2+ S ↓+2HCl (generates reactive hydrogen)
FeCl2+H2=Fe+2HCl (generates reactive hydrogen)
2FeCl3+3H2=2Fe+6HCl (generates reactive hydrogen)
Fe+S=FeS
H2S=H2+ S (the catalysed curing hydrogen of ferrous sulfide decomposes, and generates reactive hydrogen)
On the one hand, sulphur is reacted with hydrogen generates hydrogen sulfide, and concentration of hydrogen sulfide increases, and increases catalytic hydrogenation gasification reaction
Hydrogen pressure, increase the effective collision number and contact area of hydrogen and coal dust, effectively facilitate hydrogenation reaction.Iron chloride
(FeCl3) reacted with hydrogen or hydrogen sulfide, more reactive hydrogen is all generated, the progress of coal hydrogenation gasification reaction is promoted.On the other hand,
Iron chloride (FeCl3) by hydrogen reducing at fe, fe reacts with sulphur in the case of a high temperature generates ferrous sulfide (
Two catalyst), the generation of ferrous sulfide promotes the decomposition of hydrogen sulfide, generates more reactive hydrogens, further promotes hydrogasification
Reaction rate improves efficiency of carbon con version and Product yields.
In the case that catalytic hydrogenation gasification hydrogen-rich and catalysis reaction generate a large amount of reactive hydrogens exist, generation coal hydrogenation gas
Change reaction, generates synthesis gas, oil product and a part of residue.Main hydrogasification reaction equation is as follows:
C+H2→ CnHm (n >=1, m >=2, such as CH4 synthesis gas)
CxHy+H2→ CxHy+r (x >=6, y >=6, r >=2, such as benzene oil product)
After the high-temperature gas mixture of synthesis gas and oil product that catalytic hydrogenation gasification reaction generates and the heat exchange of room temperature hydrogen, using
Gas-liquid refrigerated separation realizes the separation of synthesis gas and oil product, obtains oil product, after the synthesis gas isolated is using desulfurization, obtains clean
Net synthesis gas, while sulphur is obtained, a part of the sulphur returns to coal dust pretreatment.
After catalytic hydrogenation gasification reaction, catalyst composition is converted to ferrous sulfide by initial iron chloride, and vulcanization is sub-
Iron fusing point at 1200 DEG C, be higher than catalytic hydrogenation gasification reaction temperature, therefore, at reaction conditions, catalyst with solid state with
Semicoke is mixed into residue.
Residue containing the second catalyst, regenerates through overpickling, generates iron chloride (FeCl3) solution and H2S gas.To reduce
The concentration of impurity ion content and the ferric chloride solution for ensuring to generate after pickling, the preferred hydrochloric acid of acid used in pickling.Pickling is anti-
It should be as follows:
FeS+HCl→FeCl3+H2S↑
After residue pickling, the iron chloride (FeCl of generation3) solution be sent into ferric chloride solution electrolytic cell be used for Electrowinning hydrogen
Gas and chlorine, the hydrogen sulfide gas desulfurization process that pickling generates generate sulphur, which returns to coal dust pretreatment.
Chlorine, scrap iron powder and the sulphur of the technology utilization electrolytic hydrogen production gas voluntarily synthesize under the conditions of catalytic hydrogenation reaction
Effective iron chloride and ferrous sulfide, enhance catalytic hydrogenation gasification result, reduce the cost of outsourcing finished catalyst, together
When, the conversion being made up of catalyst, realize catalyst and residue efficiently separate and circular regeneration.
Example two
Carry out the electrolysis of calcium chloride solution, wherein the concentration of calcium chloride solution preferably 80%~saturation, cell reaction formula is such as
Under:
CaCl2+2H2O=Ca (OH)2↓+Cl2↑+H2↑
The room temperature hydrogen that electrolysis obtains is mixed with the hydrogen (magnitude of recruitment is determined according to catalytic hydrogenation reaction needs) of supplement,
And heat is carried out with high temperature (for example, the 1000-1100 DEG C) gaseous mixture of the synthesis gas and oil product that are escaped by catalytic hydrogenation gasification reaction
Exchange.
The chlorine that electrolytic chlorination calcium solution obtains pre-processes into coal dust, absorbs moisture entrained by a part of coal dust, and
With lime stone (CaCO3) reaction generation chlorination calcium catalyst, wherein specific reaction are as follows:
Cl2+H2O=HCl+HClO
2HCl+CaCO3=CaCl2+CO2+H2O
In the catalytic hydrogenation gasification reactor of high temperature and pressure (1000~1100 DEG C, 10~30MPa), chlorination calcium treating adds
While hydrogen gasification reaction, by hydrogen reducing at simple substance calcium, simple substance calcium generates calcium sulfide (CaS) with sulfur reaction again, further
Promote the progress of catalytic hydrogenation gasification reaction.Main catalyzed side reaction formula is as follows:
S+H2=H2S (generates reactive hydrogen)
CaCl2+ H2=Ca ↓+2HCl (generates reactive hydrogen)
Ca+S=CaS
H2S=H2+ S (the catalysed curing hydrogen of calcium sulfide decomposes, and generates reactive hydrogen)
Sulphur is reacted with hydrogen generates hydrogen sulfide；Calcium chloride (CaCl2) reacted with hydrogen, more reactive hydrogen is generated, coal is promoted
The progress of hydrogasification reaction；Calcium chloride (CaCl2) by hydrogen reducing at simple substance calcium, simple substance calcium occurs with sulphur in the case of a high temperature
Reaction generates calcium sulfide, and the generation of calcium sulfide promotes the decomposition of hydrogen sulfide, generates more reactive hydrogens, further promote hydrogenation
Change reaction rate, improves efficiency of carbon con version and Product yields.
After catalytic hydrogenation gasification reaction, catalyst composition is converted to calcium sulfide by initial calcium chloride, and calcium sulfide is molten
O'clock at 2400 DEG C, it is higher than catalytic hydrogenation gasification reaction temperature, therefore, at reaction conditions, catalyst is with solid state and semicoke
It is mixed into residue.
Residue containing catalyst, regenerates through overpickling, generates calcium chloride (CaCl2) solution and H2S gas.Pickling is reacted such as
Under:
CaS+2HCl=CaCl2+H2S↑
After residue pickling, the calcium chloride (CaCl of generation2) solution be sent into ferric chloride solution electrolytic cell be used for Electrowinning hydrogen
Gas and chlorine, the hydrogen sulfide gas desulfurization process that pickling generates generate sulphur, which returns to coal dust pretreatment.
Example three
Carry out the electrolysis of copper chloride solution, wherein the concentration of copper chloride solution preferably 80%~saturation, cell reaction formula is such as
Under:
CuCl2+2H2O=Cu (OH)2↓+Cl2↑+H2↑
The chlorine that electrolytic chlorination copper solution obtains pre-processes into coal dust, absorbs moisture entrained by a part of coal dust, and
It is reacted with copper scrap powder (CuO) and generates copper chloride catalyst, wherein specific reaction are as follows:
Cl2+H2O=HCl+HClO
2HCl+CuO=CuCl2+H2O
In the catalytic hydrogenation gasification reactor of high temperature and pressure (1000~1100 DEG C, 10~30MPa), copper chloride catalysis adds
While hydrogen gasification reaction, by hydrogen reducing at elemental copper, elemental copper generates cuprous sulfide (Cu with sulfur reaction again2S), into one
Step promotes the progress of catalytic hydrogenation gasification reaction.Main catalyzed side reaction formula is as follows:
S+H2=H2S (generates reactive hydrogen)
CuCl2+H2=Cu ↓+2HCl (generates reactive hydrogen)
Cu+S=Cu2S
H2S=H2+ S (the catalysed curing hydrogen of cuprous sulfide decomposes, and generates reactive hydrogen)
Sulphur is reacted with hydrogen generates hydrogen sulfide；Copper chloride (CuCl2) reacted with hydrogen, more reactive hydrogen is generated, coal is promoted
The progress of hydrogasification reaction；Copper chloride (CuCl2) by hydrogen reducing at elemental copper, elemental copper occurs with sulphur in the case of a high temperature
Reaction generates cuprous sulfide, and the generation of cuprous sulfide promotes the decomposition of hydrogen sulfide, generates more reactive hydrogens, further promotes to add
Hydrogen reaction rate improves efficiency of carbon con version and Product yields.
After catalytic hydrogenation gasification reaction, catalyst composition is converted to cuprous sulfide by initial copper chloride, and vulcanization is sub-
Copper fusing point at 1130 DEG C, be higher than catalytic hydrogenation gasification reaction temperature, therefore, at reaction conditions, catalyst with solid state with
Semicoke is mixed into residue.
Residue containing catalyst, regenerates through overpickling, generates copper chloride (CuCl2) solution and H2S gas.To reduce impurity
The concentration of ion concentration and the copper chloride solution for ensuring to generate after pickling, the preferred hydrochloric acid of acid used in pickling.Pickling is reacted such as
Under:
Cu2S+4HCl=2CuCl2+2H2S↑
After residue pickling, the copper chloride (CuCl of generation2) solution be sent into ferric chloride solution electrolytic cell be used for Electrowinning hydrogen
Gas and chlorine, the hydrogen sulfide gas desulfurization process that pickling generates generate sulphur, which returns to coal dust pretreatment.
Example four
Carry out the electrolysis of bromide solutions, wherein the concentration of bromide solutions preferably 80%~saturation, cell reaction formula is such as
Under:
ZnBr2+2H2O=Zn (OH)2↓+Br2↑+H2↑
It is electrolysed the bromine gas that bromide solutions obtain, is pre-processed into coal dust, absorbs moisture entrained by a part of coal dust, and
It is reacted with zinc powder (ZnO) and generates Zinc Bromide catalyst, wherein specific reaction are as follows:
Br2+H2O=HBr+HBrO
2HBr+ZnO=ZnBr2+H2O
In the catalytic hydrogenation gasification reactor of high temperature and pressure (1000~1100 DEG C, 10~30MPa), zinc bromide catalysis adds
While hydrogen gasification reaction, by hydrogen reducing at simple substance zinc, simple substance zinc generates zinc sulphide (ZnS) with sulfur reaction again, further
Promote the progress of catalytic hydrogenation gasification reaction.Main catalyzed side reaction formula is as follows:
S+H2=H2S (generates reactive hydrogen)
ZnBr2+H2=Zn ↓+2HBr (generates reactive hydrogen)
Zn+S=ZnS
ZnBr2+H2S=ZnS ↓+2HBr (generates reactive hydrogen)
H2S=H2+ S (the catalysed curing hydrogen of zinc sulphide decomposes, and generates reactive hydrogen)
After catalytic hydrogenation gasification reaction, catalyst composition is converted to zinc sulphide by initial zinc bromide, and zinc sulphide is molten
O'clock at 2830 DEG C, it is higher than catalytic hydrogenation gasification reaction temperature, therefore, at reaction conditions, catalyst is with solid state and semicoke
It is mixed into residue.
Residue containing catalyst, regenerates through overpickling, generates zinc bromide (ZnBr2) solution and H2S gas.To reduce impurity
The concentration of ion concentration and the bromide solutions for ensuring to generate after pickling, the preferred hydrochloric acid of acid used in pickling.Pickling is reacted such as
Under:
ZnS+2HBr=ZnBr2+H2S↑
After residue pickling, the zinc bromide (ZnBr of generation2) solution be sent into bromide solutions electrolytic cell be used for Electrowinning hydrogen
Gas and bromine gas, the hydrogen sulfide gas that pickling generates are sent into desulfurizing tower, generate sulfide, it is pre- which returns to coal dust
Processing.
On the other hand the embodiment of the present invention additionally provides a kind of coal catalytic hydrogenation gasification installation, referring to Fig. 4, the coal catalysis
Hydrogasification device includes: storage sulphur device, coal dust pretreatment unit 2 and catalytic hydrogenation gasification reactor 3, the coal dust pretreatment
The feed inlet of device 2 is connected to the discharge port of the storage sulphur device, and the coal dust pretreatment unit 2 is configured to coal dust, first
Catalyst and sulphur mixing, or by coal dust, the first catalyst and sulfide mix, the catalytic hydrogenation gasification reactor 3 into
Material mouth is connected to the discharge port of the coal dust pretreatment unit 2.
The first catalyst, coal dust and the sulfide that coal dust pretreatment unit 2 mixes, or even there are also other impurities to be delivered to institute
State and carry out hydrogasification reaction in catalytic hydrogenation gasification reactor 3, wherein during specific hydrogasification, coal dust be passed through
Gasifying agent (oxygen, hydrogen) synthetic reaction occurs under the action of the first catalyst, while hydrogen can also be urged described first
Agent is restored, but since the obtained transiting metal oxidation of reduction can be obtained the second catalyst again by sulfide, coal dust after
Continue under the catalytic action of first catalyst and the second catalyst, generates synthesis gas, oil product.It is generated by itself conversion
Second catalyst avoids the phenomenon that catalyst content is reduced, and itself conversion can reduce process costs, and economic benefit is obvious.
In some embodiments, in order to which scene synthesizes first catalyst, the coal catalytic hydrogenation gasification installation is also wrapped
Include: transistion metal compound supplementary device 9, acid dip pickle 4 and electrolytic cell 1, the transistion metal compound supplementary device 9 go out
Material mouth is connected to the feed inlet of the coal dust pretreatment unit 2；The feed inlet and the catalytic hydrogenation of the acid dip pickle 4 gasify
The solid phase discharge port of reactor 3 is connected to, and the feed inlet of the electrolytic cell 1 is connected to the liquid phase discharge port of the acid dip pickle 4, institute
The halogen gas discharge port for stating electrolytic cell 1 is connected to the feed inlet of the coal dust pretreatment unit 2.Due to gasifying in catalytic hydrogenation
When reaction, the fusing point of the second catalyst of generation is higher than the temperature of catalytic hydrogenation gasification reaction, so the second catalyst meeting
Exist with solid phase, mixed with semicoke be imported into acid dip pickle 4 carry out pickling, by the solution after pickling be delivered in electrolytic cell 1 into
Row electrolysis, final electrolysis obtains hydrogen and halogen gas, and halogen gas can be used as the raw material of the first catalyst.
Specifically, by coal dust, halogen gas, transistion metal compound and sulfide, or by coal dust, halogen gas, transition
Metallic compound and sulphur import in the coal dust pretreatment unit 2 water mixed, in halogen gas, coal dust and transition gold
Belong to compound reaction and generate the first catalyst, and the importing of halogen gas, can loose coal dust, with increase coal dust and generate the
The contact area of one catalyst is uniformly mixed the first catalyst with coal dust, final to improve hydrogasification efficiency.
Referring to Fig. 4, the coal catalytic hydrogenation gasification installation further include: heat exchanger 5, cooler and 6 desulfurizing towers 7, it is described to change
The air inlet of hot device 5 is connected to the gas phase discharge port of the catalytic hydrogenation gasification reactor 3, the gas outlet of the heat exchanger 5 with
The feed inlet of the cooler 6 is connected to, and the air inlet of the heat exchanger 5 is also connected to the hydrogen discharge port of the electrolytic cell 1；Institute
The feed inlet for stating desulfurizing tower 7 is connected to the gas phase discharge port of the cooler 6, the sulfide discharge port of the desulfurizing tower 7 and institute
State the feed inlet connection of coal dust pretreatment unit 2.Wherein, specific working principle is above-mentioned has been described, and details are not described herein.
In some embodiments, it may not be necessary to which the storage sulphur device will directly using desulfurizing tower 7 as storage sulphur device
Sulfide derived from desulfurizing tower 7 is delivered in the coal dust pretreatment unit 2, simplifies the structure of whole device.
In some embodiments, for the ease of satisfaction to the different demands of the content of hydrogen, further includes: mend hydrogen production device 8, institute
It states benefit hydrogen production device 8 to be connected to the air inlet of the heat exchanger 5, mends the low temperature hydrogen importing heat exchanger 5 that hydrogen production device 8 is discharged and carry out heat
Exchange obtains high-temperature hydrogen, then by high-temperature hydrogen by carrying out catalytic hydrogenation gasification reaction in catalytic hydrogenation gasification reactor 3,
To reduce the energy consumption of catalytic hydrogenation gasification reactor 3.
In the description of this specification, particular features, structures, materials, or characteristics can be real in any one or more
Applying can be combined in any suitable manner in example or example.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (12)
1. a kind of coal catalytic hydrogenation gasification process characterized by comprising
Coal dust pretreatment: mixing by coal dust, the first catalyst and sulphur, or by coal dust, the first catalyst and sulfide, to be made
Coal dust intermixture, wherein first catalyst is transition metal halide, contains moisture in the coal dust；
Catalytic hydrogenation gasification: the coal dust intermixture obtained is subjected to catalytic hydrogenation gasification, contains synthesis gas and oil to be made
The gaseous mixture of product, the residue containing semicoke and the second catalyst；Wherein, in catalytic hydrogenation gasification, first catalysis
Agent is reacted with hydrogen generates transition metal, and the transition metal is reacted with the sulphur or sulfide again generates the second catalyst,
Second catalyst is transient metal sulfide.
2. coal catalytic hydrogenation gasification process according to claim 1, which is characterized in that the pretreated specific mistake of coal dust
Journey are as follows:
Coal dust, halogen gas, transistion metal compound and sulphur are mixed, or by coal dust, halogen gas, transistion metal compound
With sulfide mix, wherein the halogen gas and water reaction generate hydrogen halides, the hydrogen halides again with the transition metal
It closes object reaction and generates the first catalyst, first catalyst, the coal dust and the sulphur or first catalyst, institute
It states coal dust and the sulfide is mixed to get coal dust intermixture.
3. coal catalytic hydrogenation gasification process according to claim 2, which is characterized in that also wrapped after the catalytic hydrogenation gasification
It includes:
Residue pickling: will be obtained described containing the progress pickling of the residue of semicoke and the second catalyst, transition metal halogen is made
Compound solution and hydrogen sulfide；
The electrolysis of transition metal halide solution: the transition metal halide solution obtained is electrolysed, hydrogen and halogen is made
Gas, wherein the halogen gas in the coal dust pretreatment is the halogen gas that the transition metal halide solution is electrolysed
Body.
4. coal catalytic hydrogenation gasification process according to claim 3, which is characterized in that molten in the transition metal halide
In liquid electrolytic process: the concentration of the transition metal halide solution is more than or equal to 80%.
5. coal catalytic hydrogenation gasification process according to claim 3, which is characterized in that in the residue acid cleaning process,
Using oxygen-free acid as pickling solution.
6. coal catalytic hydrogenation gasification process according to claim 3, which is characterized in that in the residue acid cleaning process,
The concentration of the pickling solution used is 10%~15%.
7. coal catalytic hydrogenation gasification process according to claim 1, which is characterized in that also wrapped after the catalytic hydrogenation gasification
It includes:
Gas-liquid refrigerated separation: by it is obtained it is described contain the gaseous mixture of synthesis gas and oil product carry out gas-liquid separation；
Desulfurization process: isolated synthesis gas is subjected to desulfurization process, and in the sulphur or sulfide that desulfurization process is obtained
At least partly sulphur or sulfide be returned in coal dust pretreatment.
8. coal catalytic hydrogenation gasification process according to claim 1, which is characterized in that also wrapped after the catalytic hydrogenation gasification
It includes:
Gaseous mixture heat exchange: hydrogen and the catalytic hydrogenation gasification gaseous mixture obtained are subjected to heat exchange, then will be after heat exchange
Hydrogen be returned in catalytic hydrogenation gasification.
9. coal catalytic hydrogenation gasification process according to claim 1, which is characterized in that in the catalytic hydrogenation gasification
In: the vapor pressure of the catalytic hydrogenation gasification is 10~30MPa, and gasification temperature is 1000~1100 DEG C.
10. a kind of coal catalytic hydrogenation gasification installation characterized by comprising
Store up sulphur device；
Coal dust pretreatment unit, the feed inlet of the coal dust pretreatment unit is connected to the discharge port of the storage sulphur device, described
Coal dust pretreatment unit is configured to mix in coal dust, the first catalyst and sulphur, or coal dust, the first catalyst and sulfide are mixed
It closes；
Catalytic hydrogenation gasification reactor, the feed inlet of the catalytic hydrogenation gasification reactor and the coal dust pretreatment unit go out
Material mouth connection.
11. coal catalytic hydrogenation gasification installation according to claim 10, which is characterized in that the coal catalytic hydrogenation gasification dress
It sets further include:
Transistion metal compound supplementary device, the discharge port and the coal dust of the transistion metal compound supplementary device pre-process
The feed inlet of device is connected to；
Acid dip pickle, the feed inlet of the acid dip pickle are connected to the solid phase discharge port of the catalytic hydrogenation gasification reactor；
Electrolytic cell, the feed inlet of the electrolytic cell are connected to the liquid phase discharge port of the acid dip pickle, the halogen of the electrolytic cell
Gas discharge mouth is connected to the feed inlet of the coal dust pretreatment unit.
12. coal catalytic hydrogenation gasification installation described in 0 or 11 according to claim 1, which is characterized in that the coal catalytic hydrogenation gas
Makeup is set further include:
Cooler, the feed inlet of the cooler are connected to the gas phase discharge port of the catalytic hydrogenation gasification reactor；
Desulfurizing tower, the feed inlet of the desulfurizing tower are connected to the gas phase discharge port of the cooler, the sulphur of the desulfurizing tower or
Sulfide discharge port is connected to the feed inlet of the coal dust pretreatment unit.
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