Embodiment
The inventor is through extensive and deep research; Keep that the processing costs of fixed bed pressured gasification stove raw material is low, thermo-efficiency is high, the raw material suitability is widely under the prerequisite of advantage; After the synthetic gas of being produced is carried out rough purification through solid phase separation circuit, Quench washing procedure; Through non-catalytic partial oxidation synthetic gas medium high carbon compound, low carbon compound (methane etc.) are transformed; Realize purifying synthetic gas, simplify follow-up processing flow, practice thrift investment and working cost, a kind of method of High-efficient Production synthetic gas is provided.Accomplished the present invention on this basis.
Among this paper, said " biomass " comprise plant-animal and mikrobe, for example are to reject edible part other the material that is rich in biomass energy afterwards, like vegetable fibre, xylogen particle.Concrete example comprises various vegetations (comprising aquatic each kind of plant), the city wood waste, and farm crop cauline leaf root, nutshell, the wooden waste material in paper mill, sawdust pressed the waste material that tankage and forest lumbering after oil or the sugar produce, or the like.The main composition composition of these biomass for example is saccharan Mierocrystalline cellulose and semicellulose, and the xylogen of poly aromatic compound.
Among this paper, described " coal material " comprises the various coals that are used to produce synthetic gas in this area.Compound method of the present invention for example can be used the Shanxi hard coal but be not limited thereto.
Among this paper, described " synthetic rough product " is to be mixed into the synthetic gas to be clean that raw material obtains with biomass and optional coal material.Particularly, be raw material with biomass, biomass and coal blending, the mixing proportion of biomass can feed intake from 0~100% arbitrary proportion.Comprise higher carbon compounds, low carbon compound (methane etc.) in the said synthetic gas.Generally include the above alkene alkanes component of C2 in the said higher carbon compounds, comprise that also other formation solid phases are carried secretly, the organism of tar part.Said low carbon compound mainly comprises methane.
Among this paper, described " tar component " is ubiquitous component in the synthetic rough product, is known to those skilled in the art.
Among this paper, said " solid phase is carried secretly " is ubiquitous component in the synthetic rough product, is known to those skilled in the art.
Among this paper, described " cracking, hydrogenation and conversion " is method well known to those skilled in the art.
Among this paper, the method that described final dusting adopts usually comprises cyclonic separator, cooling scrubber etc.
Technical conceive of the present invention is following:
The present invention be directed to solid phase in the synthetic rough product that is produced with fixed-bed gasification furnace, tar, methane, alkene alkane and other treatment of organic matters of organic process method, key is the combination of the process operation unit of the fixed bed pressured gasification that adopted, the washing of synthetic gas Quench and synthetic gas non-catalytic partial oxidation.
Particularly; With biomass and coal material is raw material; Adopt fixed bed pressured gasification to produce synthetic gas; And the solid phase of passing through synthetic gas is removed, the synthetic gas Quench is washed and the coupling of non-catalytic partial oxidation technology, realizes the rough purification of synthetic gas, has simplified conventional fixed bed pressure gasification process synthetic gas purified process; Make the technology that is adopted be convenient to industrialized realization and application.Can realize that biomass and coal are that raw material is gasifying under the operating mode of different feeds ratio in the fixed bed pressured gasification stove, produce and supply the required synthetic gas of downstream Chemical Manufacture.
A kind of fixed bed pressured gasification preparing synthetic gas method of the present invention comprises:
(a) be mixed into raw material with biomass and optional coal material, synthetic rough product is provided in the fixed bed pressured gasification unit;
(b) in the condensation separation unit, removing in the synthetic rough product solid phase carries secretly; And the synthetic coal-tar middle oil component of rough product carried out condensation separation, the synthetic rough finished product that is purified;
(c) the synthetic rough product of said purification carries out cracking, hydrogenation and conversion in the non-catalytic partial oxidation unit, makes its staple be converted into carbon monoxide and hydrogen, the synthetic gas after obtaining transforming;
(d) in post-processing unit, the synthetic gas after transforming is carried out aftertreatment, obtain the synthetic gas product.
In an embodiment, above-mentioned is raw material with biomass, biomass and the blending of coal material, and the method that adopts fixed bed pressured gasification to produce synthetic gas comprises at least one cover fixed bed pressured gasification stove; At least one Quench washing tower, gas-liquid separator, washing water recycle pump, tar transferpump; At least one non-catalytic partial oxidation stove.
After the present invention is employed in and adopts behind the fixed bed pressured gasification output synthetic gas Quench washing procedure that tar component is carried out condensation separation; To synthesize in rough product alkene alkanes component C2 more than and other organism with oxygen as oxygenant through the non-catalytic partial oxidation operation and carry out cracking, hydrogenation and conversion, make that main ingredient is converted into carbon monoxide and hydrogen in the synthetic gas.Synthetic gas after the conversion is sent into subsequent conversion and desulfurization and decarburization operation and the composition of synthetic gas is adjusted with synthetic gas is made with extra care purification.Simplify the purification and the refining flow of the synthetic rough product of fixed bed, reduced the purification and the purified difficulty of synthetic gas.
Synthetic simultaneously rough product is sent into the non-catalytic partial oxidation operation after separating the rough purification with tar separation through solid phase, the design difficulty of minimizing non-catalytic partial oxidation stove burner, has reduced applying working condition, more helps the long-period stable operation of producing; The removing of solid phase impurity and tar reduced on-catalytic and do not sealed the probability that the oxidation operation solid phase byproduct produces, and avoided increasing the requirement of follow-up final dusting.
Through the coupling of condensation separation unit (washing of synthetic gas Quench) and non-catalytic partial oxidation technology, realize the rough purification of synthetic gas, simplify conventional fixed bed pressure gasification process synthetic gas purified process.This combination can realize that biomass and coal are that raw material is gasifying under the operating mode of different feeds ratio in the fixed bed pressured gasification stove, produce to supply the required synthetic gas of downstream Chemical Manufacture.This means that technology of the present invention goes for various raw materials and carries out synthetic gas production, making present production unit can not need adjust can use.
Below detail to various aspects of the present invention:
Fixed bed pressured gasification step (a)
The present invention is applicable to that with biomass, biomass and the blending of coal material be raw material, and the mixing proportion of biomass can feed intake from 0~100% arbitrary proportion; Adopt fixed bed pressured gasification, produce synthetic gas as vaporized chemical with pure oxygen and oxygen enrichment.In the subsequent step, carry out the rough purification processing of synthetic gas with non-catalytic partial oxidation operation coupling after synthetic gas process solid phase separation of being produced and the tar separation.
Preferably, in described " fixed bed pressured gasification ", the biomass material of employing certain grain size or biomass and coal blended feedstock (arbitrary proportion), pure oxygen or oxygen enrichment are produced crude synthesis gas (also promptly synthetic rough product) as vaporized chemical, slag tap mode.
Particularly for example, said fixed bed pressured gasification unit is the fixed bed pressured gasification stove.
It is that the synthetic gas that the fixed bed gasification technology of any ingredient proportion of raw material is produced carries out Chemical Manufacture that the present invention is applicable to biomass and coal material, can simplify the purification of synthetic gas and the processing requirement of refining step, reduces the cost of investment of purification and process for purification.Severe day by day in petroleum-based energy supply at present, coal material and biomass material be developed day by day and application as the gasification technology of substitute energy and raw material.The fixed bed pressured gasification technology progressively obtains paying close attention to, develops and uses as traditional sophisticated coal gasification substance technology.Employing of the present invention will have actual application prospect comparatively widely.
Condensation separation step (b)
Condensation separation step (b) is included in the condensation separation unit to be removed in the synthetic rough product solid phase and carries secretly; And the synthetic coal-tar middle oil component of rough product carried out condensation separation, the synthetic rough finished product that is purified.
Condensation separation of the present invention unit is to carrying solid phase secretly in the synthetic rough product and tar component separates and condensation.Said condensation separation unit adopts Quench washing device (or being called Quench washing unit).
In an embodiment, said Quench washing unit comprises Quench washing tower, gas-liquid separator, washing water recycle pump, tar transferpump.Particularly, the Quench washing room adopts the cooling of Quench washing tower spray washing, through gas-liquid separator condensed tar is separated with synthetic gas with the technology washings.
Adopt the Quench washing process that the coal-tar middle oil component of synthetic gas is carried out refrigerated separation, avoid causing side reactions such as carbon deposit because tar gets into the non-catalytic partial oxidation unit, therefore need not increase the secondary separation method carries out gas solid separation once more; Tar can return vapourizing furnace through gasifier nozzle and gasify once more.
Send into the non-catalytic partial oxidation operation after the rough purification of synthetic rough product through the Quench washing process, reduce non-catalytic partial oxidation stove burner design difficulty, reduced applying working condition, more help the long-period stable operation of producing; Removing of solid phase impurity and tar reduced the probability that non-catalytic partial oxidation operation solid phase byproduct produces, and avoided increasing the requirement of follow-up final dusting.
Be sent to the on-catalytic receiver at the Quench washing room after coal-tar middle oil components condense is separated with synthetic gas and remove methane and alkene alkanes gas in the synthetic gas, the reforming gas that is produced can pass through conventional conversion and can be sent to synthesis unit with purification and carry out Chemical Manufacture.
The object of the invention is the technical process of adopting invention to adopt, and simplifying with any ingredient proportion coal material and biomass is raw material, the purification and the treating process of the employing synthetic gas that fixed bed gasification produced.
Non-catalytic partial oxidation step (c)
Carry out the rough purification processing of synthetic gas with non-catalytic partial oxidation operation coupling after synthetic gas process solid phase separation of being produced and the tar separation.
In a preference; In the said non-catalytic partial oxidation unit; To synthesize in the rough product alkene alkanes component more than the C2 and other organism with oxygen as oxygenant and carry out cracking, hydrogenation and conversion, make that main ingredient is converted into carbon monoxide and hydrogen in the synthetic gas
Particularly, non-catalytic partial oxidation partly adopts pure oxygen as oxygenant.Tar from going out returns fixed-bed gasification furnace, and react the combustion zone that sprays into vapourizing furnace through burner again, and the circulation of washing water clear liquid is used for the washing of raw gas.Isolated tar returns fixed-bed gasification furnace, and react the combustion zone that sprays into vapourizing furnace through burner again, and the circulation of washing water clear liquid is used for the washing of rough coal material gas.
The present invention is owing to increased the non-catalytic partial oxidation unit; The alkene alkanes component that C2 is above and other organism are that oxygenant transforms in the non-catalytic partial oxidation unit at pure oxygen; Reforming gas is formed be mainly carbon monoxide and hydrogen, reduced the separation circuit of back system methane and alkene alkanes composition.
Carry out solid phase at synthetic rough product and separate the back and adopt the Quench washing process to avoid tar to bring the non-catalytic partial oxidation unit into, reduce non-catalytic partial oxidation stove burner design difficulty, reduced applying working condition, more help the long-period stable operation of producing; Removing of solid phase impurity and tar reduced the not probability of part chemical industry preface solid phase byproduct generation of on-catalytic, avoided increasing the requirement of follow-up final dusting.More help the realization of industrial applications.
The present invention has adopted the combination of fixed bed pressured gasification, the washing of synthetic gas Quench and non-catalytic partial oxidation technology; With the Quench washing process the coal-tar middle oil component of synthetic gas is carried out refrigerated separation, avoid causing side reactions such as carbon deposit because tar gets into the non-catalytic partial oxidation unit, therefore need not increase the secondary separation method carries out gas solid separation once more.
Post-processing step (d)
Particularly, said post-processing unit comprises subsequent conversion unit and desulfurization and decarburization unit.
Particularly, said post-processing unit can not contain the final dusting method.
Particularly, the synthetic gas after the conversion is sent into subsequent conversion and desulfurization and decarburization operation and the composition of synthetic gas is adjusted with synthetic gas is made with extra care purification.Simplify the purification and the refining flow of the synthetic rough product of fixed bed, reduced the purification and the purified difficulty of synthetic gas.
Described subsequent conversion unit can adopt the conventional converter unit of this area, only otherwise goal of the invention of the present invention is produced restriction to get final product.
Described desulfurization and decarburization unit can adopt the conventional equipment of this area, only otherwise goal of the invention of the present invention is produced restriction to get final product.
Specify like nothing, various raw materials of the present invention all can obtain through commercially available; Or prepare according to the ordinary method of this area.Only if definition or explanation are arranged in addition, the same meaning that all specialties used herein and scientific words and those skilled in the art are familiar with.Any in addition with the institute similar content of putting down in writing or the equalization method and material all can be applicable in the inventive method.
Other aspects of the present invention are because the disclosure of this paper is conspicuous to those skilled in the art.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, or carries out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all umbers are weight part, and all per-cents are weight percentage, and described polymericular weight is a number-average molecular weight.
Only if definition or explanation are arranged in addition, the same meaning that all specialties used herein and scientific words and those skilled in the art are familiar with.Any in addition with the institute similar content of putting down in writing or the equalization method and material all can be applicable in the inventive method.
Embodiment 1~5
Synthetic rough product is realized the rough purification to synthetic gas through following operation after fixed-bed gasification furnace is seen off:
A, adopt the Quench washing that synthetic rough product temperature is reduced, the solid phase of carrying secretly in the synthetic rough product is separated and the tar component condensation;
B, the synthetic rough product after Quench washing cooling adopt the non-catalytic partial oxidation technology; With the pure oxygen is that oxygenant transforms methane, alkene alkane and other organism in the synthetic rough product, makes the organic content of reforming gas medium high carbon and low-carbon (LC) satisfy the requirement of follow-up synthetic production.
C, reforming gas carry out heat recuperation after conversion section is regulated the ratio of carbon monoxide and hydrogen in the synthetic gas through waste heat boiler;
D, conversion gas remove hydrogen sulfide and excess carbon dioxide gas in the synthetic gas through the desulfurization and decarburization operation;
E, synthetic gas process compression section raising synthetic gas pressure through purifying;
F, high pressure synthetic gas get into synthesizing section and carry out reacted.
This technology makes an experiment to process data through method for testing in setting up and verifies.
Present method can realize the synthetic gas output of following each operating mode:
Methane content≤0.3mol% in the synthetic gas.
This operational path is not limited only to listed operating mode, and wherein the ingredient proportion of biomass material and coal material can be adjusted arbitrarily.
The ingredient proportion of present most of fixed bed biomass in biomass and coal mixed material feeding generally is no more than 15%; Technology adjustment the biomass material and the multifuel combustion operating mode of coal to adapt to different ratios of present technique through necessity, the suitable downstream of output produce needed synthetic gas.
Discuss:
The object of the invention is the technical process of adopting invention to adopt, simplifies the purification and the treating process of the synthetic gas that is produced with coal material and biomass material fixed bed gasification.
It is that raw material carries out pressurized gasification in fixed-bed gasification furnace that the present invention adopts with biomass and coal material, the gasification gas of being produced through the Quench washing, tar removes with the pure oxygen condition under the flow process coupling production synthetic gas of non-catalytic partial oxidation.
Have following characteristics:
(1) be the processing of the fixed bed pressured gasification outlet of still that adopts gasification gas can be at first means through the Quench washing solid phase in the gasification gas is carried secretly and tar component condensation and removing;
(2) the gasification gas after rough purification transforms organic constituents such as the methane in the synthetic gas, alkene alkane through pure oxygen or oxygen enrichment non-catalytic partial oxidation, produces the synthetic gas that satisfies production requirement.
(3) raw material of fixed bed pressured gasification is the blended feedstock of biomass material and biomass and coal material; Adopt pure oxygen, oxygen enrichment to produce as oxygenant.
(4) carry out sending into synthesizing section after boosting through the synthetic gas compression section in adjustment that synthetic gas forms and refining back through conversion section, desulfurization and decarburization workshop section through the synthetic gas behind the non-catalytic partial oxidation and carry out industrial production.
The above is merely preferred embodiment of the present invention; Be not in order to limit essence technology contents scope of the present invention; Essence technology contents of the present invention is broadly to be defined in the claim scope of application, and if any technological entity or method that other people accomplish are defined identical with the claim scope of application; Also or a kind of change of equivalence, all will be regarded as and be covered by among this claim scope.
All documents in that the present invention mentions are all quoted as a reference in this application, are just quoted such as a reference separately as each piece document.Should be understood that in addition that after having read foregoing of the present invention those skilled in the art can do various changes or modification to the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.