CN109776260A

CN109776260A - A method of methanol is prepared using volatile matter in low-order coal

Info

Publication number: CN109776260A
Application number: CN201910089171.9A
Authority: CN
Inventors: 薛安克; 王建中; 王再富; 俞天明; 吕彬峰
Original assignee: Zhejiang Tianlu Environmental Technology Co Ltd
Current assignee: Zhejiang Tianlu Environmental Technology Co Ltd
Priority date: 2019-01-30
Filing date: 2019-01-30
Publication date: 2019-05-21

Abstract

The present invention provides a kind of methods for preparing methanol using volatile matter in low-order coal, low-order coal passes sequentially through stoving process and gasification reducing process handles to obtain rich gas, rich gas be purified by purification process after rich gas, gasification reducing process be the chemical reaction process heated under anaerobic or micro-oxygen conditions to the low-order coal after drying；Purified rich gas passes sequentially through thick sulfur removal technology, the first compression process and fine desulfurizing technology and handles to obtain reforming unstripped gas；Reforming unstripped gas obtains reforming gas by reforming process；Reforming gas mends one or more of carbon, shift conversion and benefit hydrogen technique by decarburization and obtains the methyl methanol syngas that hydrogen-carbon ratio R value is 2.05~2.1；Methyl methanol syngas obtains crude carbinol and methanol purge gas by the second compression process, methanol synthesizing process, and crude carbinol obtains product methanol by methanol rectification technique.The present invention prepares methanol, and production cost is low, and the volatile matter in low-order coal is substantially effectively utilized.

Description

A method of methanol is prepared using volatile matter in low-order coal

Technical field

The present invention relates to volatile matters in coal substance clean utilization technical field more particularly to a kind of utilization low-order coal to prepare first The method of alcohol.

Background technique

China is the country of a rich coal, oil-poor, few gas, and consumption of coal accounts for 60% or more of non-renewable energy consumption figure, Which dictates that the energy resource structure based on coal is difficult to change within the quite a long time.From explored coal mine quality It sees, low-order coal proportion is very big in coal in China, thus low-order coal production high-quality chemical industry in rationally and efficiently utilizing Product is particularly important.In recent years, the continuous development of the technologies such as coal gasification, pyrolysis of coal, gas purification and coal gas separation, It utilizes the clean and effective of middle low-order coal and has obtained more and more attention.

Methanol is basic Organic Chemicals and solvent, and is chemical products, its purposes in basic organic chemical industry It is only second to ethylene, propylene and benzene etc..Methanol has very important status and extremely extensive purposes in Chemical Manufacture, main It is used to manufacture a variety of organic products such as formaldehyde, acetic acid, chloromethanes, first ammonia, dimethyl sulfate, alkene and pesticide, medicine One of important source material.The deep processed product of methanol is up to more than 120 kinds at present, be widely used in chemical industry, light industry, communications and transportation, The industries such as medicine, weaving.

Methanol is prepared using good coal such as anthracite, although the yield of methanol is higher, production cost compared with It is high.And much the poor quality of middle low-order coal, ash content are high, water content is high in China, prepare methanol using low-order coal, can reduce methanol Production cost.Usually crude coal gas will be obtained after low order pyrolysis of coal, general pyrolysis is that having a large amount of oxygen (or air) Under the conditions of carry out, a part of low-order coal will react in oxygen and be used for heat supply and produce a large amount of CO when pyrolysis₂.Due to CO₂It cannot burn, belong to invalid gas, and because of oxy combustion, nitrogen content is excessively high in crude coal gas, reduces crude coal H in gas₂With CO energy density, reduce crude calorific value of gas, other than return combustion, the pyrolysis crude coal gas difficulty of output has other Economic value.And coal gasification course is the biggest problems are that underuse the chemical constituent contained in coal, it cannot be by it Molecule all interrupts production CO, H₂, then carry out chemically synthetizing methanol.And the reduction of low order coal gasification, reforming technique and methanol-fueled CLC Technology then can to greatest extent be remained the chemical constituent in coal in the form of methanol.

Summary of the invention

In view of this, in view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of utilize in low-order coal to volatilize The method for point preparing methanol, the hydro carbons by the reduction acquisition volatile matter that gasifies in the low-order coal after dry, then in will volatilize point Etc. CO and H needed for reforming acquisition methanol-fueled CLC raw material₂Methanol is prepared, production is greatly saved in low raw-material cost Cost, the impurity in prepared methanol is few, and quality is high, and the volatile matter in low-order coal is substantially effectively utilized.

In order to solve the above technical problems, the present invention provides the following technical scheme that

A method of methanol being prepared using volatile matter in low-order coal, is comprised the following steps that:

(1) low-order coal passes sequentially through stoving process and gasification reducing process handles to obtain rich gas, and the rich gas passes through purification Technique be purified after rich gas, the purified rich gas include CO, CO₂、H₂And hydro carbons, the gasification reducing process be The chemical reaction process that the low-order coal after drying is heated under anaerobic or micro-oxygen conditions；

(2) purified rich gas described in step (1) passes sequentially through sulfur removal technology and the first compression process handles to obtain weight Turn over unstripped gas；

(3) reforming unstripped gas described in step (2) is obtained by reforming process comprising CO, CO₂And H₂'s Reforming gas；

(4) reforming gas described in step (3) passes through selected from decarburization mend carbon technology, shift conversion technique and benefit hydrogen technique One or more of obtain methyl methanol syngas, the hydrogen-carbon ratio R value of the methyl methanol syngas is 2.05~2.1；

(5) methyl methanol syngas described in step (4) passes sequentially through the second compression process, methanol synthesizing process obtains crude carbinol And methanol purge gas, the crude carbinol pass through methanol rectification technique again and obtain product methanol.

Stoving process is by moisture removal most in low-order coal, low-order coal and exhaust gas after being dried, after drying Low-order coal enters gasification reducing process and reacts to obtain the rich gas of high temperature and the upgraded coal with certain temperature.Gasification reduction The source of oxygen is mainly in the following several ways in the anaerobic or micro- oxygen environment that technique uses: (1) sky, inside raw material low-order coal Gap, the air of the gap entrainment between material and material；(2) it is mixed into from leakages such as feed inlet, the discharge ports of gasification reducing process A small amount of air；(3), Coal Quality percentage is accounted for hereinafter, can slightly be passed through in gasification reducing process in explosion limit value 5% O₂Or (air), further preferably it is passed through the O for accounting for Coal Quality percentage 3%₂Or (air), be conducive to improve Temperature, the slagging prevention etc. for the reduction reaction that gasifies, and ensure that the safety and stability of entire gasification reducing process reaction simultaneously Property；It is preferred that the low-order coal after drying carries out gasification reduction reaction in oxygen-free environment, the low-order coal after avoiding drying is entering gas Change the low-order coal after drying in reducing process reaction process and combustion reaction occurs for oxygen, generates a large amount of aphlogistic CO₂, CO in rich gas to guarantee obtained high temperature₂Volume basis it is smaller, be conducive to the subsequent rich gas for preparing high-energy density, work Skill step is few, simple to operation, so that reaction can carry out safely.

Contain CO, H in the rich gas of high temperature₂、CO₂, hydro carbons, dust, coal tar, naphthalene, vapor, unsaturated hydro carbons and sulfur-bearing Compound etc. removes the impurity such as solid dirt, tar, naphthalene and vapor by purification process, thus the richness after being purified Gas.The resources, especially coal tar such as coal tar, waste water can be recycled during purification, be the important by-product of low-order coal. Purified rich gas passes sequentially through sulfur removal technology and the first compression process handles to obtain reforming unstripped gas.Sulfur removal technology wraps again Thick sulfur removal technology and thick sulfur removal technology are included, purified rich gas tentatively removes most of sulfur-containing compound by thick sulfur removal technology, So that H₂S is removed to 20mg/Nm³Below；Gas pressure is improved by the first compression process again, continues to take off using fine desulfurizing technology Except the sulfur-containing compound in purified rich gas, the total sulfur in purified rich gas is taken off into 0.1ppm hereinafter, preventing Containing Sulfur It closes object and causes the catalyst poisoning in subsequent technique, reach the catalyst and methanol synthesizing process of subsequent reformation conversion process Requirement of the catalyst to sulfur content.In addition, antichlor and decarbonylation Base Metal chemical combination can be added simultaneously in fine desulfurizing technology desulfurization The cleanser of object is by these harmful substance removals, to prevent methanol synthesis catalyst poisoning and deactivation.

Reforming unstripped gas mainly includes CO, CO₂、H₂And hydro carbons, it is well known that CO and H₂It can be closed directly as chemical industry At level-one raw material, hydro carbons then needs reforming to generate CO and H₂, therefore will be reforming using reforming technique Part hydrocarbon reformation converts to obtain comprising CO and H in unstripped gas₂Reforming gas, it is reforming after CO in reforming gas And H₂Total percent by volume increases, and is conducive to the amount for improving subsequent methanol-fueled CLC raw material.

Active principle in methyl methanol syngas needed for methanol-fueled CLC is H₂、CO、CO₂, to hydrogen-carbon ratio in methyl methanol syngas It is required that there is following formula: R=(H₂-CO₂)/(CO+CO₂), wherein the theoretical value of the hydrogen-carbon ratio R value of methyl methanol syngas is 2.0, optimum value 2.05-2.1.And the hydrogen-carbon ratio R value in the reforming gas of above-mentioned preparation generally can not be just met for R value circle In 2.05-2.1, therefore utilize through one of decarburization mend carbon technology, shift conversion technique and benefit hydrogen technique or several tune The hydrogen-carbon ratio R value that the hydrogen-carbon ratio of whole reforming gas makes to obtain methyl methanol syngas is adjusted to 2.05~2.1.

Finally, methyl methanol syngas obtains crude carbinol and methanol purge gas by the second compression process, methanol synthesizing process, institute It states crude carbinol and product methanol is obtained by methanol rectification technique.The rate of recovery of rectification process about 99.5%, the impurity of gained methanol Few, quality is high, and refined methanol specification meets GB338-2011 high-class product methanol quality index request.Present industrialized production first Alcohol is substantially with smokeless coal gasification at synthesis gas, then methanol processed, and the anthracitic unit cost price of raw material is in 1200-1500 member/T Left and right, 1T coal produce about 0.77T methanol, and the unit cost price of raw material low-order coal of the invention is in 80~100 yuan/T, low Volatile matter content is in 20~55wt% in rank coal, and by 1T low-order coal in terms of, the yield using volatile matter methanol in low-order coal is 15%.As shown in table 1 below, it is far below using the unit cost price for the methanol that low-order coal is raw material preparation using anthracite as raw material The unit cost price of the methanol of preparation, thus using the present invention in method prepare methanol greatly reduced raw material at This expenditure.In addition, by-product upgraded coal and coal tar, upgraded coal also can be obtained in the technique for preparing methanol using low-order coal Unit price be 500-600 member/T；The unit price of coal tar is 2000-2500 member/T, the product of upgraded coal and coal tar Value is high.

The unit cost price comparison's table for the methanol that table 1 is prepared using anthracite and low-order coal as raw material

Title	Cost of material (yuan/ton)	The methanol output (ton) of preparation	The methanol unit cost price (yuan/ton) of preparation
				Anthracite	1200-1500	0.77	1558-1948
Low-order coal	80-100	0.15	533-667

Preferably, sulfur removal technology described in step (2) includes fine desulfurizing technology and thick sulfur removal technology, the purified richness Gas passes sequentially through thick sulfur removal technology, the first compression process and fine desulfurizing technology and handles to obtain reforming unstripped gas.Thick desulfurization work The cooperation of skill, fine desulfurizing technology, so that the sulfur-bearing total amount of purified rich gas is preferably minimized as far as possible.

Preferably, reforming gas described in step (4) first passes through shift conversion technique and obtains conversion gas, the conversion gas Methyl methanol syngas is obtained by the decarburization mend carbon technology again.Shift conversion technique are as follows: CO+H₂OH₂+CO₂If reforming CO too high levels in gas, hydrogen is less, by vapor (H₂O it) is passed through in reforming gas and makes CO and H₂Shift conversion occurs for O Technique, in this way operation can increase the amount of active principle hydrogen.It may cause CO after shift conversion technique₂It is extra, but CO₂Compare It is easy removing.Generally determine the choice of shift conversion technique according to the R value of reforming gas, general R value is close to 2.05-2.1 When, without shift conversion technique, R value is quickly directly adjusted by subsequent decarburization mend carbon technology；R value is much smaller than 2.05- When 2.1, increase shift conversion technique, R value is increased with this.

Preferably, decarburization mend carbon technology described in step (4) is when the hydrogen-carbon ratio R value of the reforming gas is greater than 2.1 When, it is passed through CO₂, so that R value is adjusted to 2.05-2.1；When the hydrogen-carbon ratio R value of the reforming gas is less than 2.05, removing CO₂, so that R value is adjusted to 2.05-2.1.Decarburization mend carbon technology includes decarbonization process and mend carbon technology, that is, removes and supplement CO₂, Successively achieve the purpose that the hydrogen-carbon ratio for adjusting reforming gas.

Preferably, the shift conversion technique be during reforming unstripped gas to methyl methanol syngas by CO by with H₂O response transform is converted into H₂.In reforming technical process, there is H in reforming unstripped gas₂O (vapor) is existing In the case of, with certain side reaction, side reaction is mainly CO and H₂O (vapor) shift conversion H₂Reaction.

Preferably, benefit hydrogen technique described in step (4) is that H is added during reforming gas to methyl methanol syngas₂'s Technique.The H of supplement₂What but the external world was directly bought, it is also possible to the H recycled from subsequent methanol purge gas₂, reforming gas If R value it is too small, H₂It can directly be supplemented into reforming gas.The H that can also will be recycled from subsequent methanol purge gas₂ As in the second compression process in circulating air supplement machine.

Preferably, purification process described in step (1) includes dust collecting process and detar technique.Contain in the rich gas of high temperature A large amount of dust, coal tar, naphthalene and vapor etc.；First with dust collecting process dedusting, the temperature of the rich gas in dust removal process is prevented It reduces, coal tar and vapor etc., which are condensed into liquid and adhere to a large amount of dusts, causes subsequent technique line clogging, and dedusting is caused to imitate Fruit decline；It should be containing the substance that a large amount of naphthalenes and tar etc. are easily solidifying or easily crystallize, if these substances not removed as far as possible in rich gas It goes, will cause damages to subsequent handling or even jeopardizes the safety of whole device.Therefore, using detar process, to remove The substance that naphthalene, tar that subsequent handling causes damages etc. may be easily coagulated or easily crystallized.Purification process can also include removing naphthalene work Skill utilizes the content that naphthalene in rich gas is further decreased except naphthalene technique.In addition, purification process may also include hydrogenation technique, if rich Volume fraction in gas containing unsaturated hydrocarbons is excessively high, is translated into saturated hydrocarbons using hydrogenation technique, prevent unsaturated hydrocarbons decarburization and The problems such as causing carbon distribution.

Preferably, the reaction temperature of gasification reducing process described in step (1) is 350-800 DEG C.At this temperature, it dries The volatile matter in low-order coal afterwards is escaped from low-order coal, so that the rich gas of high temperature is obtained, it is remaining solid after the reduction reaction that gasifies Body residue is the upgraded coal with temperature, and the volatile matter content in upgraded coal is 8-15wt%.Wherein, gasification reducing process can be with For level-one, or multistage.When using level-one gasification reducing process, primarily to the rich gas of most of high temperature is obtained, The height of temperature directly affects the temperature of subsequent gas production, the yield of upgraded coal and level-one upgraded coal；It is gone back when using multistage gasification When original process, multistage gasification reducing process main function is the solids that can not gasify in upper level gasification reducing process Matter (including the fine coal after gasification, solid impurity etc.), a certain amount of similar pitch etc. that can not gasify within certain residence time Higher boiling grease continues gasification and the residence time short has little time to be precipitated or phenolic compound, fragrant hydrocarbonylation is not achieved in temperature The polycondensation reaction condition of object etc. is closed, gasification that the reaction was continued is conducive to improve gas yield.

Reforming unstripped gas is that gas each component is not in reforming unstripped gas through the reforming technique of some hydrocarbon It is directly that some hydrocarbon is reforming for CO and H through separating₂Hydrocarbon conversion technique because reforming purpose only be The hydrocarbon conversion is generated into CO and H₂, and itself contained some CO and H in reforming unstripped gas₂, there is no need to by hydrocarbon Class separates hydro carbons from reforming unstripped gas and carries out the reforming of hydro carbons again, saves work using such operation Skill step, high financial profit.

Reforming technique mainly includes steam reformation conversion, steam pure oxygen is reforming and pure oxygen is reforming.Steam It is reforming, steam purity oxygen is reforming is required to catalyst, the catalyst of reforming technique is mostly supported catalyst Agent, active component are mainly that Ni, Co, Fe, Cu etc. be nonmetallic and the noble metals such as Rh, Ru, Pt.It is reforming to generally require heat supply, It can be by the way of direct heating or indirect heating.Reforming steam purity oxygen is using pure oxygen (oxygen) and one Divide hydrocarbon fuel direct heating, reaction temperature is made to reach 850-1300 DEG C, under the effect of the catalyst, reforming raw material Some hydrocarbon in gas is reacted with vapor generates CO and H₂；Using extraneous heat supply when steam reformation converts, reach temperature It 850-1200 DEG C, reacts some hydrocarbon and vapor in reforming unstripped gas and generates CO And H₂；The key reaction mechanism of two methods are as follows:

CmHn+mH₂O=mCO+1/2 (n+2m) H₂Main reaction, the endothermic reaction

With CH₄For, key reaction equation CH₄+H₂O→CO+3H₂, the H of generation₂Molar ratio with CO is 3:1, than Example is larger, and to preparing, reforming gas is highly beneficial.

Pure oxygen is reforming for pure oxygen to be passed through in reforming unstripped gas, key reaction mechanism are as follows: CH₄+1/2O₂→CO+ 2H₂, the H of generation₂Molar ratio with CO is 2:1, is conducive to prepare reforming gas.Other hydro carbons and methane and O in addition to methane₂ Reaction mechanism it is similar.

It is preferred, therefore, that reforming unstripped gas described in step (3) is reforming original through reforming process Expect that gas each component is without isolation in gas, directly by some hydrocarbon in the reforming unstripped gas it is reforming for CO and H₂Reforming technique.Preferably, the reforming technique be selected from steam reformation conversion, steam pure oxygen it is reforming and Pure oxygen is reforming one such or several.

Preferably, the pressure of the first compression process described in step (2) is 20-25kg, and temperature is 300-400 DEG C.Essence is de- Sulphur technique is generally dry desulfurization, can operate under a certain pressure, so that the effective component of the sulphur in the unit volume of processing increases Height, sulfur content removal rate also greatly improve, while can be substantially reduced the device of fine de-sulfur, while improving the utilization rate of equipment.

Preferably, the pressure 40-50kg of the second compression process described in step (5), temperature are 200-350 DEG C.Second pressure Contracting technique be in order to adjustment methyl methanol syngas the conditions such as pressure and temperature, be conducive to carry out methanol-fueled CLC under low pressure Reaction.

Based on above technical scheme, method in the present invention, by the way that gasification reduction volatile matter will be obtained in low-order coal, then will CO and H needed for the reforming acquisition methanol-fueled CLC raw material such as the hydro carbons in volatile matter₂, to prepare methanol, the impurity in methanol Few, quality is high, and the volatile matter in low-order coal is substantially effectively utilized, and manufactures methanol feedstock and enrich, and cost is relatively low, greatly Production cost, but also the rich upgraded coal and coal tar for producing high value are saved greatly, meet state coal comprehensive utilization direction.

Detailed description of the invention

It, below will be in embodiment in order to illustrate more clearly of embodiment in the present invention or technical solution in the prior art Required attached drawing is briefly described, it should be apparent that, the accompanying drawings in the following description is only one recorded in the present invention A little embodiments are also possible to obtain other drawings based on these drawings for those of ordinary skill in the art.

Fig. 1 is a kind of the first flow diagram of method that methanol is prepared using volatile matter in low-order coal；

Fig. 2 is a kind of second of flow diagram of method that methanol is prepared using volatile matter in low-order coal.

Specific embodiment

Next combined with specific embodiments below invention is further explained, but does not limit the invention to these tools Body embodiment.One skilled in the art would recognize that present invention encompasses may include in Claims scope All alternatives, improvement project and equivalent scheme.

In the present invention, if not refering in particular to, used raw material and equipment etc. are commercially available or commonly used in the art. Method in following embodiments is unless otherwise instructed the conventional method of this field.Term " first ", " in the present invention Two " etc. are only used for distinguishing description, are not understood to indicate or imply relative importance.

As shown in Figs. 1-2, the invention discloses a kind of method for preparing methanol using volatile matter in low-order coal, this include with Lower processing step；

A method of methanol is prepared using volatile matter in low-order coal, it is characterised in that: is comprised the following steps that:

Raw material low-order coal of the invention can be fine coal and be also possible to lump coal, when low-order coal uses lump coal, to bulk excessively Coal can be by broken, screening process to obtain the lesser fine coal of granularity.It is preferred that using fine coal as raw material, be on the one hand because It no longer needs to for fine coal through broken, screening process, saves processing step, heating surface area is big when drying, and drying efficiency is high, another party Face is that fine coal is cheap with respect to lump coal.It is preferred that being less than the fine coal of 20mm using granularity, still further preferably it is less than using granularity The fine coal of 6mm.

Volatile matter content is generally 20%-55% in low-order coal, and the content of tar is 3%-15% or so, and fixed carbon contains Amount is 30%-60%, the content of water is 10%-40%, remaining as dust and other impurities.The degree of coalification of low-order coal is low, but Contain petroleum resources abundant, the volatile matter being rich in low-order coal is highly beneficial to synthesis gas is extracted, therefore preferably volatile matter exists Low-order coal between 30%-55%.

Drying can only generally remove most Free water in low-order coal, and cannot remove the combination water in low-order coal, because This, low-order coal by stoving process handle after dry after low-order coal and exhaust gas, gained dry after low-order coal still contain There is a certain amount of moisture, the moisture of this some residual can gasify in subsequent gasification reducing process becomes vapor.If low order Contain a large amount of moisture in coal, heat consumption is big during will lead to gasification reduction reaction, and therefore, technical solution of the present invention is first Choosing is handled the portion of water first removed in low-order coal by stoving process to low-order coal.The drying medium of stoving process It can be flue gas or vapor, drying can be divided into directly drying and indirect drying.When using flue gas as medium is dried, though Right flue gas is highest with the efficiency for the drying that low-order coal directly contacts, but flue gas is used to want strict control when being dried The percent by volume of oxygen is in explosion limit hereinafter, to prevent detonation, the efficiency of flue gas indirect drying in stoving process environment It is unsatisfactory, therefore for production safety and drying efficiency, preferably vapor is dried.Vapor, which is directly dried, to be easy to be possible to Cause vapor to be mixed into provide with the consumption in low-order coal, not only causing reaction coal resource, reduces drying efficiency, therefore Using the drying mode of vapor indirect drying low-order coal, to prevent the moisture in water steam from entering in low-order coal.In addition, drying If water vapour pressure is excessive during dry, vapor bring temperature is excessively high to be easy to cause during the drying process, in low-order coal Part volatile matter can escape, and the evolution of one side volatile matter can bring security risk, on the other hand will affect subsequent gasification The gas production of reducing process, thus in drying course dry steam pressure be not easy it is excessive, with guarantee both can guarantee drying effect, It can guarantee that the volatile matter in low-order coal is not gasified again.It is preferred, therefore, that stoving process uses water vapour indirect drying, water The pressure of steam is 0.3-1.5Mpa, and the temperature of water vapour is 105-250 DEG C, not only prevents the O in external air₂It is mixed Enter to consume coal substance, and can maximumlly reduce the moisture content in low-order coal under this process condition, it might even be possible to so that 7wt% is reduced to hereinafter, most moisture is adjoint at this time from the water content in the low-order coal that the discharge port of stoving process is discharged The fugitive dusts such as coal dust escaped from low-order coal, and as water vapor into the exhaust gas generated after drying, stoving process Outlet mass temperatures be 50-150 DEG C；Still further preferably, when the pressure of vapor is 0.6-1.2Mpa, the temperature of vapor When degree is 120-200 DEG C, after drying the moisture content of low-order coal will decrease to 6wt% hereinafter, stoving process outlet mass temperatures It is 80 DEG C -130 DEG C.

Stoving process of the invention can be level-one, or it is multistage, because if low-order coal after level-one stoving process Moisture content still reach to the requirement less than technique, can be continued using multistage dry such as second level drying, three-level stoving process into one Drying is walked, until the moisture content of low-order coal meets process conditions after drying.In addition, multistage stoving process can connect and set Setting can also be arranged in parallel, and can reinforce drying effect when connecting using multistage stoving process, can increase drying work when in parallel The treating capacity of skill, therefore according to the demand of actual production technique is series connection or in parallel or in series simultaneously to multistage stoving process In conjunction with when design, can be adjusted according to the actual situation, as long as identical technical effect can be reached, specifically, than Such as, when the inlet amount of stoving process is in terms of the low-order coal of 20-30t/h, level-one steam drying technique can be used；Work as stoving process Inlet amount in terms of the low order of 50-70t/h, second steam stoving process can be used, in this way it is more economical rationally.

Low-order coal after being dried by stoving process enters to gasification reducing process and is reacted, for one into one optimization work Skill, low-order coal after the drying can also add gasification feeding process before entering gasification reducing process, so as to low after drying Rank coal rapidly enters gasification reducing process, increases the surface area of material, is conducive to accelerate gasification reduction reaction.

Wherein, gasification reducing process is that the chemistry that is heated under anaerobic or micro-oxygen conditions to the low-order coal after drying is anti- Answer technique.Low-order coal after drying enters gasification reducing process, under the heating of the heat mediums such as flue gas, nothing in reaction process Other substances such as additive need to be added, temperature is generally 350 DEG C -800 DEG C, complex chemical reaction occurs under pressure≤30Kpa Process obtains the rich gas of solid carbon and high temperature, wherein solid carbon is upgraded coal, the volatile matter 8- in upgraded coal 15wt%.The rich gas of high temperature is to include CO, H₂、CO₂, hydro carbons, coal tar, naphthalene, halide, dust and sulfur-containing compound etc. it is more Foreign gas.

Wherein, the source of gasification reducing process uses anaerobic or micro- oxygen environment oxygen is mainly in the following several ways: (1), Gap inside raw material low-order coal, the air of the gap entrainment between material and material, the O in the air of this part₂Gasifying It is reacted immediately with coal in the environment of reducing process high temperature and generates CO₂Or CO；(2) from the feed inlet of gasification reducing process, discharging The mixed a small amount of air of the leakage such as mouth, the oxygen of this partial air, the micro O in this part₂In gasification reducing process high temperature It is reacted immediately with coal under environment and generates CO₂Or CO；(3), in explosion limit value hereinafter, can slightly lead in gasification reducing process Enter to account for the O of Coal Quality percentage 5%₂Or (air), 1. this operation, which has the advantage that, can be improved gasification reduction work Temperature and capacity usage ratio in skill；2. improving the conversion ratio of charcoal；3. preventing coal coking；4. a small amount of O₂It is endless with low-order coal Full burning produces more CO, brings more synthesis gas to be subsequent.Since gasification reducing process internal temperature is higher, The a small amount of O being passed through₂Moment can occur oxidation reaction (including combustion reaction), and the burning point of many combustibles is all anti-in gasification reduction Below the reaction temperature answered.Because CO mixes with air explosion limit 12%~74.2%；H₂Explosion value is 4%-75%.O₂Duty gas Ratio is 21%.The explosion limit upper value of pure oxygen is 6% or so after conversion.By theoretical calculation, the coal of 100kg can be generated about 80Nm³CO and H₂.So being passed through the O for accounting for Coal Quality percentage 5%₂It is safe；Still further preferably, it is passed through and accounts for coal The O of charcoal mass percent 3%₂, with the security and stability for the reducing process reaction that ensures entirely to gasify.But when gasification reduction is anti- When the temperature answered meets technique requirement, it can not also be passed through oxygen, the low-order coal after preferably drying gasifies in oxygen-free environment Reduction reaction, so that reaction can carry out safely.

Wherein, gasification reducing process can be level-one, or multistage.It is main when using level-one gasification reducing process If the rich gas of most of high temperature, the height of temperature directly affect subsequent gas production, the yield of upgraded coal and level-one in order to obtain The temperature of upgraded coal, the reaction temperature for the reducing process that gasifies are 350 DEG C -800 DEG C, and the volatile matter content in upgraded coal is 8- 15wt%, further preferably, the reaction temperature for the reducing process that gasifies are 400-750 DEG C；Still further preferably 450-700 DEG C.When When using multistage gasification reducing process, multistage gasification reducing process main function is the nothing in upper level gasification reducing process Method gasification solid matter (including gasification after fine coal, solid impurity etc.), it is a certain amount of can not within certain residence time gas The higher boilings grease such as similar pitch changed continues gasification and the residence time short has little time precipitation or phenol generalization is not achieved in temperature The polycondensation reaction condition of object, arene compound etc. is closed, gasification that the reaction was continued is conducive to improve gas yield and upgraded coal Quality.The unit price of upgraded coal is generally 500-600 member/T, and the upgraded coal after gasification reduction can be used for selling.

Other than the temperature of guarantee gasification reducing process is reasonable, while it must also guarantee certain in gasification reducing process stop The time is stayed, the residence time is too short, and volatile matter also not evolution gasification completely while influencing gas yield, more influences upgrading The quality of coal；Residence time is too long, although product is guaranteed, yield is not caught up with, so keeping a reasonable gasification The reduction reaction residence time is most important to product yield and quality.It is general to gasify since the kind of raw material low-order coal is different The residence time of material is 30min-4h in reducing process.

Preferably using two-stage gasification reducing process in the present invention, the material after stoving process drying is introduced into level-one gasification also Original process enter back into second level gasification reducing process, and the low-order coal after drying is introduced into level-one gasification reducing process and obtains level-one gas Body and level-one solid, level-one solid, which enters back into second level gasification reducing process, to be continued gasification and obtains secondary gas and second level solid, and two Grade solid is upgraded coal；The feeding temperature of level-one gasification reducing process is 80 DEG C -120 DEG C, and air outlet temperature is 180 DEG C -550 DEG C, reaction temperature is 450 DEG C -650 DEG C, and drop temperature is 350 DEG C -600 DEG C；The charging temperature of the second level gasification reducing process Degree be 350 DEG C -600 DEG C, drop temperature be 450 DEG C -750 DEG C, reaction temperature be 550 DEG C -800 DEG C, air outlet temperature be 450 DEG C - 700℃.When using two-stage gasification reducing process, primarily to most of volatile is made to be gasified totally, it can obtain big The gas of amount can obtain the lower upgraded coal of volatile matter again, and wherein the volatile matter content in upgraded coal is 3-8wt%.

The rich gas of gasification reducing process preparation can be using a portion as fuel, and for example, stoving process is either subsequent Reforming technique provide heat, realize heat supply oneself it is self-sustaining, without using extraneous fuel heat supply.

Methanol synthesis catalyst also has very high requirement to the impurity content in methyl methanol syngas, otherwise, the longevity of catalyst Life will be reduced, and the quality of methanol will reduce.Therefore, purified treatment is had to pass through to methyl methanol syngas, the task of purification is just It is to remove sulfide, oil, water, grit, carbonyl iron and chloride etc. contained therein.Wherein, sulphur is particularly importantly removed Compound.

In the rich gas for the high temperature being discharged from gasification reducing process other than useful ingredient, also containing other some nocuousness Impurity, such as dust, tar, vapor, unsaturated hydro carbons and naphthalene, these impurity, which must exist, has seriously affected methanol conjunction At the normal production of technique, therefore, these objectionable impurities must also be purified to defined standard.

The rich gas of high temperature obtained from gasification reducing process enters purification process so as to the rich gas after being purified.Purify work Skill includes dust collecting process and detar technique etc..Rich gas includes successively CO, H through dust collecting process and detar technique₂With hydro carbons Purified rich gas.Contain a large amount of dust, coal tar, vapor, sulfur-containing compound etc. in the rich gas of high temperature；First with removing The dedustings such as dirt device prevent the temperature of the rich gas in dust removal process from reducing, and coal tar and vapor etc. are condensed into liquid and adhere to A large amount of dusts cause subsequent technique line clogging, and dust removing effects is caused to decline；It should be containing a large amount of naphthalenes and tar etc. easily in rich gas Substance that is solidifying or easily crystallizing will cause damages to subsequent handling or even jeopardize entire dress if these substances not removed as far as possible The safety set.Therefore, the tar in rich gas is taken off to≤1mg/Nm using detar technique³, cooling for example, by using cooling tower The substances such as a large amount of vapor and naphthalene, the grease obtained after cooling can also be condensed while gaseous coal tar in rich gas Mixture passes through water-oil separating again can be obtained byproduct coal tar.The unit price of coal tar is 2000-2500 member/T, rich The value of the coal tar of production is higher.It is further preferred that purification process further includes passing through detar process except naphthalene technique Remaining gas, which enters, afterwards removes naphthalene technique, and the naphthalene in rich gas is taken off to≤4mg/Nm³.Except naphthalene technique include Processing Method for Washing Naphthalene Used of Light Tar, Carbolineum washes naphthalene and regeneration except naphthalene and regeneration, rich oil.In this technique, vaporization at high temperature point can be respectively obtained similar by cooling step by step The coal tar of the coal tar of the different temperatures boiling range such as diesel oil, gasoline, light petrol, similar light petrol boiling range is light tar. Because of light tar abundant raw material, it is preferred that Processing Method for Washing Naphthalene Used of Light Tar can reach qualified synthesis gas.It is further preferred that Purification process further includes hydrogenation technique, and hydrogenation technique may choose whether according to presence of unsaturates in rich gas plus hydrogen, the present invention Contain a certain amount of alkene in the rich gas of middle preparation, while preventing alkene is reforming from easily causing to tie carbon problem, it is therefore desirable to set Set hydrogenation technique.Hydrogenation technique is mainly realized by hydrogenation catalyst, common are cobalt molybdenum hydrogenation catalyst, iron molybdenum adds hydrogen Catalyst is passed through a certain amount of hydrogen, under the effect of the catalyst, alkene is made to be transformed into alkane.

Sulfide is easy to cause reforming catalyst and methanol synthesis catalyst poisoning and deactivation, therefore in reforming work It needs to remove the sulfide in purified rich gas before skill.Purified rich gas, will be purified into the processing of thick sulfur removal technology H in rich gas₂S is removed to 20mg/Nm³Below.Thick sulfur removal technology uses wet method crude desulfurization, and Wet Flue Gas Desulfurization Technology is gas-liquid Reaction, reaction speed is fast, and desulfuration efficiency is high, is generally higher than 90%, technology maturation is widely applicable.Wet Flue Gas Desulfurization Technique compares Maturation, production run is safe and reliable, in numerous desulfurization technologies, occupies leading position always, accounts for desulfurization total installation of generating capacity 80% or more.Therefore, a large amount of H in rich gas is first tentatively taken off in wet desulphurization₂S removing.

Using wet method crude sulfur removal technology, general device can not operate under a certain pressure, and the tolerance because of processing is caused not have Compression is flowed through large-minded, and occupation area of equipment and package unit are also larger.And the sulfur-bearing total amount of the gas after thick desulfurization is not It is able to satisfy the requirement of subsequent reformation reforming catalyst and methanol synthesis catalyst to sulfur content.Therefore, after thick sulfur removal technology processing Gas first pass through the first compression process processing improve gas pressure, enter back into fine desulfurizing technology, the pressure of the first compression process For 20-25kg, temperature is at 300~400 DEG C.Fine desulfurizing technology is generally dry desulfurization, can operate, make under a certain pressure The effective component for the sulphur in unit volume that must be handled increases, and sulfur content removal rate also greatly improves, while can be substantially reduced essence The device of desulfurization, while improving the utilization rate of equipment.

Enter fine desulfurizing technology processing through the compressed gas of the first compression process, obtains reforming unstripped gas.Essence is de- Sulphur technique is dry desulfurization, is to remove sulfide using solid desulfurating agent.Thick sulfur removal technology takes off most sulfide It removes, remaining a small amount of sulfide is that it is reduced to 1mg/Nm by desulfurizing agent³Hereinafter, not only reducing in fine desulfurizing technology The cooperation of sorbent consumption, Er Qiejing, thick desulfurization twice technique is the reliable means of high-precision desulfurization, is reduced as far as possible Sulfur-bearing total amount in purified rich gas meets subsequent reformation reforming catalyst and methanol synthesis catalyst to sulfur content It is required that.

Dry desulfurization is divided into three types according to its property and desulphurization mechanism: hydrogenation type reforming catalyst, such as iron-molybdenum, nickel- Molybdenum etc., absorption-type convert absorbent, such as ZnO, iron oxide, manganese oxide, absorbent-type, such as active carbon, molecular sieve.For example, this The H of generation is absorbed using iron molybdenum catalytic hydroconversion organic sulfur (COS) in invention and with ZnO desulfurizing agent₂S, by purified richness Total sulfur in gas takes off 0.1ppm hereinafter, preventing sulfide from causing the catalyst poisoning in subsequent technique, reaches subsequent reformation and turns The requirement of the catalyst of chemical industry skill and the catalyst of methanol synthesizing process to sulfur content.For example, at a temperature of 300~400 DEG C, Absorb using the organic sulfur in the purified rich gas of iron molybdenum catalytic hydroconversion and with ZnO desulfurizing agent the H generated₂S will be purified The total sulfur in rich gas afterwards takes off 0.1ppm hereinafter, reaching reforming catalyst and methanol synthesis catalyst to sulfur content It is required that.

Leading to the substance of methanol synthesis catalyst poisoning and deactivation, there are also chloride and carbonyl metal compounds etc..In fine de-sulfur In technique, the cleanser of antichlor and decarbonylation metal carbonyl compound can be added simultaneously by these harmful substance removals.Chloride containing closes Object is easily reacted with metal ion, is easy to make the permanent poisoning of metal ion, is generally carried out dry method dechlorination, dechlorination using antichlor The main component of agent is basic anhydride, such as CaO, ZnO and Na₂O etc., chlorine in the purified rich gas obtained after purification Content is less than 0.1 × 10^-6.O.1x10 carbonyl metal compound needs in methyl methanol syngas are removed to^-6Hereinafter, metal carbonyl Compound is mainly with Fe (CO)₅、Ni(CO)₄Form exist, in fine desulfurizing technology addition removing metal carbonyl cleanser with Achieve the purpose that reduce carbonyl iron, carbonyl nickel in purified rich gas.

It include H in above-mentioned reforming unstripped gas₂、CO、CO₂And hydro carbons, hydro carbons generally refer to saturated hydrocarbons, hydro carbons for Belong to inert gas for synthesizing methanol, but hydro carbons can change synthesizing methanol by reforming technique needed for H₂And CO, With the amount of this unstripped gas for increasing methanol-fueled CLC, reduce the waste of resource, improves the utilization rate of low-order coal.

Reforming technique mainly includes steam reformation conversion, steam pure oxygen is reforming and pure oxygen is reforming.

Steam reformation, which converts, steam purity oxygen is reforming is required to catalyst, and the catalyst of reforming technique is mostly Loaded catalyst, active component are mainly that Ni, Co, Fe, Cu etc. be nonmetallic and the noble metals such as Rh, Ru, Pt.Reforming one As need heat supply, can be by the way of direct heating or indirect heating.CO and H in reforming gas₂Source be two Part, a part are the CO and H that some hydrocarbon is obtained by catalyzed conversion in reforming unstripped gas₂, another part is to reform Convert original H in unstripped gas₂And CO.

Reforming steam purity oxygen is to make reaction temperature using pure oxygen (oxygen) and a part of hydrocarbon fuel direct heating Reach 850-1300 DEG C, under the effect of the catalyst, some hydrocarbon in reforming unstripped gas reacts generation with vapor CO and H₂；Using extraneous heat supply when steam reformation converts, so that temperature is reached 850-1200 DEG C, make under the effect of the catalyst Some hydrocarbon in reforming unstripped gas is reacted with vapor generates CO and H₂；The key reaction mechanism of two methods are as follows:

(1)CmHn+mH₂O=mCO+1/2 (n+2m) H₂Main reaction, the endothermic reaction

(2)Side reaction, the endothermic reaction

With CH₄For, key reaction equation CH₄+H₂O→CO+3H₂, the H of generation₂Molar ratio with CO is 3:1, than Example is larger, and to preparing, reforming gas is highly beneficial.In reforming technical process, there is H in reforming unstripped gas₂O In the presence of (vapor), with certain side reaction, side reaction is mainly CO and H₂O (vapor) shift conversion H₂'s Reaction.

Generally in the actual production process, vapor catalyzed reforming and on-catalytic reforming conversion either two is generallyd use The combination of person.

It (1) is about 1.98 using hydrogen-carbon ratio in the reforming obtained reforming gas of one section of steam depth；

(2) the reforming obtained reforming gas of reforming+two sections of pure oxygens self-heating depth of one section of steam either shallow is used Middle hydrogen-carbon ratio is about 1.31-1.98.

It (3) is about 1.31 using hydrogen-carbon ratio in the reforming obtained reforming gas of steam pure oxygen.

Active principle in methyl methanol syngas needed for methanol-fueled CLC is H₂、CO、CO₂, to hydrogen-carbon ratio in methyl methanol syngas It is required that there is following formula: R=(H₂-CO₂)/(CO+CO₂), wherein the hydrogen-carbon ratio R=(H of methyl methanol syngas₂-CO₂)/ (CO+ CO₂) theoretical value be 2.0, optimum value 2.05-2.1.Contain a certain amount of CO in methyl methanol syngas₂Synthesizing methanol can be increased to urge The catalytic activity of agent reduces the fuel factor of reaction, keeps the temperature of catalysis easily controllable, reduces catalyst and is made due to overtemperature At heat inactivation, to extend the service life of catalyst, still, CO₂Content must be appropriate.If CO₂Content it is excessive, then The content of water just will increase in product, can thus reduce the compressed capability of compressor, increase gas compression and rectification working process Energy consumption.CO₂Optimum content in methyl methanol syngas, should be according to the catalyst and methanol-fueled CLC operation temperature used in methanol-fueled CLC Degree does corresponding adjustment.

When the R value of methyl methanol syngas is greater than 2.1, represents that the more carbon of hydrogen are few, and methanol synthesis loop circulating flow rate is big at this time, follow Ring air compressor power consumption is big, and methanol purge gas amount is also big, and many unstrpped gases pass through the useful H of multiple process preparation₂、CO、 CO₂With methane etc. as methanol purge gas is sent into fuel system burn-up, the serious wasting of resources is caused, consumption of raw materials amount increases.When When the R value of methyl methanol syngas is less than 2.05, it is not able to satisfy the requirement of methanol-fueled CLC.And gained is reforming after reforming technique R value in gas is generally individually smaller than 2.05, it is therefore desirable to be adjusted to its R value.

To reforming gas R value can by decarburization mend carbon technology, variation conversion process and mend one of hydrogen technique or It is several to realize.

Decarburization mend carbon technology includes decarbonization process and mend carbon technology, i.e. removing CO₂With supplement CO₂Technique.Reforming gas The methyl methanol syngas that R value is 2.05-2.1 is obtained after handling by decarburization mend carbon technology.When the R value of reforming gas is greater than 2.1 When, it is few to represent the more carbon of hydrogen, is passed through CO into reforming gas by mend carbon technology₂Or the CO of high-purity₂, obtain standard compliant Methyl methanol syngas.When the R value of reforming gas is less than 2.05, representing hydrogen, to lack carbon more, removed by decarbonization process reforming A part of CO of gas₂, so that the R value value range of methyl methanol syngas is adjusted to 2.05-2.1.

Industrial removing CO₂Method it is very much, can generally speaking be divided into two major classes: one kind is solvent absorption, another Class is pressure swing adsorption method (PSA).Solvent absorption includes Physical Absorption method, chemical absorption method and physicochemical adsorption method, Physical Absorption method, as low-temp methanol washes method, polyglycol dimethyl ether process, propylene carbonate ester process；Chemical absorption method, generally as NaOH, KOH, Ba (OH)₂CO can be very effectively absorbed Deng the stronger lye of alkalinity₂Gas, principle are because of CO₂Gas is molten Carbonic acid is generated in water, the hydrogen ion that the ionization of carbonic acid fraction generates is reacted with the hydroxide ion in lye generates water, therefore can Remove CO₂.PSA method is or else lower with different adsorption capacities, adsorption rate and suction with partial pressure to adsorbate using adsorbent Attached power, and under a certain pressure to the characteristic for thering is selection to adsorb by each component of isolated admixture of gas, pressurized adsorbent removes Go impurities in feed gas component, these impurity of removed under reduced pressure and regenerate adsorbent, the method have simple process, operation Stablize, low energy consumption, without " three wastes " emission problem the advantages that, be a kind of de- CO of energy conservation₂New technology, have a extensive future.In addition this work The CO of the removing of skill work₂Also it can be recycled recycling.

When the R value of reforming gas is less than 2.05, can also be turned by mending hydrogen technique substitution decarbonization process to adjust to reform Change gas R value, so that R value circle is between 2.05-2.1.By the H in suitable external world₂Or the H of high-purity₂It is passed through in reforming gas, Make its R value in the range of 2.05-2.1.When reforming using one section of steam depth, resulting reforming unstripped gas Middle R value is about 1.98, the standard value of very close methyl methanol syngas, at this time H in reforming unstripped gas₂The amount lacked is less When, it can also be directly by extraneous H₂Or the H of high-purity₂It is passed through in reforming unstripped gas and finely tunes its R value, to save decarburization work Skill reduces process flow.Here H₂Or the H of high-purity₂It can be obtained from extraneous directly purchase, it can also be from subsequent methanol-fueled CLC work The H of purification is recycled after skill in remaining methanol purge gas₂, it is preferred to use the H purified from methanol purge gas₂With reforming original Material gas gas enters subsequent reforming technique together, not only realizes recycling for resource, also saves process costs branch Out.When reforming using reforming+two sections of pure oxygens self-heating depth of one section of steam either shallow or using steam pure oxygen to reform turns When change prepares reforming gas, the R value in resulting reforming gas is much smaller than 2.05, and the amount that hydrogen lacks is larger, preferably now will Purification H in methanol purge gas₂Be far from satisfying adjust reforming gas at this time needed for hydrogen amount, therefore preferably use The mode of decarburization adjusts R value.

As shown in Fig. 2, when being additionally provided with shift conversion technique between reforming technique and decarburization mend carbon technology.It is reforming Hydrogen-carbon ratio R value is generally individually smaller than 2.05 in gas, represents that the more hydrogen of carbon are few, and such component is not able to satisfy the requirement of synthesizing methanol.Carbon It is superfluous and hydrogen deficient, optimization focus on how obtaining more hydrogen.Reforming gas is obtained by shift conversion technique Conversion gas, if the hydrogen-carbon ratio of conversion gas just boundary does not need cooperation decarburization mend carbon technology and either mend in 2.05~2.1 Hydrogen technique adjusts hydrogen-carbon ratio.If the hydrogen-carbon ratio of the conversion gas obtained after shift conversion is still undesirable, convert Gas obtains methyl methanol syngas by decarburization mend carbon technology, and the hydrogen-carbon ratio R value of the methyl methanol syngas is adjusted to 2.05~2.1.

By a certain amount of H₂O (water vapour) is passed through in reforming gas, the key reaction in shift conversion technique are as follows: The fuel factor of this reaction regards H₂It is then the endothermic reaction, if water if liquid water depending on the state of O Steam is then exothermic reaction.Reacting condition is reversible reaction, and the equilibrium constant reduces with the increase of pressure.It is reforming By obtaining variation gas after shift conversion process in gas, H can be increased₂Percentage by volume, reduce the volume basis of CO Number, but will increase CO simultaneously₂, therefore also need to remove CO using decarbonization process after generally using shift conversion technique₂.According to The R value of reforming gas determines the choice of shift conversion technique, when general R value is close to 2.05-2.1, turns without transformation Chemical industry skill directly quickly adjusts R value by subsequent decarburization mend carbon technology；When R value is much smaller than 2.05-2.1, increases transformation and turn Chemical industry skill increases R value with this, and the decarburization mend carbon technology after recycling adjusts R value.Shift conversion technique is increasing effective group Divide H₂While, the CO that also increases₂Percentage by volume, but CO₂Also it is easier to remove, be become after shift conversion technique A large amount of CO in ventilation₂It can be disposed by decarburization mend carbon technology.When be using steam reformation conversion and steam purity oxygen weight It is whole when being converted reforming, a certain amount of not reacted H is contained in prepared reforming gas₂O (water vapour), variation The external supplement H of Shi Wuxu₂O (water vapour) can directly carry out shift conversion technique under certain condition.

The methyl methanol syngas obtained from decarburization mend carbon technology passes through the second compression process first and carries out compression processing, is conducive to The pressure 40-50kg of the second compression process of synthesis of subsequent methanol, temperature are 200-350 DEG C.Due to passing through the second compression process The pressure 40-50kg of treated gas uses low-pressure process synthesizing methanol.In order to realize isobaric methanol-fueled CLC, methanol is saved Synthesic gas compressor and compression power consumption reduce investment cost and production cost, and the production and purification of methyl methanol syngas are generally low Pressure carries out.Methyl methanol syngas enters methanol synthesizing process, and catalyst needed for methanol-fueled CLC is added, and obtains after reaction thick Methanol and methanol purge gas.Methanol synthesis catalyst generally can be divided into zinc chromia catalyst, copper-based catalysts, palladium series catalyst and Molybdenum series catalyst etc. is commonly copper zinc aluminium-based catalyst in industrial production.The purity of crude carbinol in the present invention is 95% left It is right.

The main chemical equation of synthesizing methanol is as follows:

Since, there are many side reactions, these side reactions generate a large amount of inert gas and in work in Production of methanol It is constantly accumulated in skill, influences the normal operation of methanol synthesizing process, it is necessary to constantly discharged, this discharge gas is known as methanol Periodic off-gases.The main component of methanol purge gas is H₂、CO、H₂O and CH₄Inert gases are waited, wherein H₂And CH₄Volumn concentration Account for about 90% or so.Using the H in pressure swing adsorption recycling methanol purge gas₂, increase yield of methanol can be reached and energy-saving and emission-reduction are double Weight purpose.The H in methanol purge gas is recycled by pressure-variable adsorption etc.₂It supplements in reforming gas, it can also will be from subsequent methanol The H recycled in periodic off-gases₂As the H in the second compression process in circulating air supplement machine, in addition recycled₂Also it can be used as fuel combustion Heat supply.Or without Pressure Swing Adsorption H₂, directly conduct in the second compression process is passed through using methanol purge gas as circulating air A part of raw material of methanol-fueled CLC.In addition in Production of methanol, the pressure of rich producing steam is generally 2.5MPa or so, this Some vapor, which can be used as present apparatus methyl alcohol synthetic reactor by-product, can be used as the vapor of steam reformation conversion in reforming technique Source, waste heat waste water reuse save this process costs expenditure.

The crude carbinol obtained from methanol synthesizing process enters methanol rectification technique and obtains product methanol.Industrial refining crude first Alcohol is broadly divided into two methods: one is the methods of physics, i.e., using different components such as methanol, water and organic impurities thick Different volatility in methanol mixed solution is isolated by distillation；Another kind is chemical method, i.e., still not by distillation The quality requirement of purification methanol can be reached, but acidic materials such as some impurity such as formic acid that must be driven off again can then pass through Caustic soda is added to be neutralized to remove.The method of two kinds of purification methanol can industrially be divided into list based on distillating method Tower, double tower, three towers and four towers totally four kinds of technique.Single column technique can be used for using fuel methanol as the essence of the crude carbinol of target product System；Double tower, three towers and four tower process are used primarily in using the high methanol of purity requirement as the purification of the crude carbinol of target product.Its In, double tower process is gradually eliminated since its energy consumption is higher with respect to three towers and four tower process, large size newly-built at present Methanol-fueled CLC factory is all made of three towers improved on the basis of double tower process and four tower process, energy consumption can compared with double tower process To reduce 30%~40%.The rate of recovery of methanol rectification technique about 99.5%, gained methanol are colourless transparent liquid, no foreign odor Taste, impurity is few, and quality is high, and refined methanol specification meets GB338-2011 high-class product methanol quality index request.

Present industrialized production methanol is substantially with smokeless coal gasification at synthesis gas, then methanol processed, the anthracitic list of raw material Position cost is in 1500 yuan/T or so, and the restriction of 1T coal takes 0.77T methanol, and the unit cost of raw material low-order coal of the invention is 80 ~100 yuan/T, in low-order coal volatile matter content in 20~55wt%, be by 1T low-order coal in terms of, utilize volatile matter system in low-order coal The yield of methanol is 15%.As shown in table 1 below, the unit cost price of the methanol prepared using low-order coal as raw material be far below with Anthracite is the unit cost price of the methanol of raw material preparation, therefore prepares methanol using the method in the present invention and greatly reduce The cost payout of raw material.In addition, in the technique for preparing methanol using low-order coal, also can be obtained by-product upgraded coal and Coal tar, the unit price of upgraded coal are 500-600 member/T, and the unit price of coal tar is 2000-2500 member/T, what richness produced Value of the product is high.

In conclusion the method in invention, by the way that gasification reduction volatile matter will be obtained in low-order coal, then will volatilize point CO and H needed for the reforming acquisition methanol-fueled CLC raw material such as hydro carbons₂, to prepare methanol, the impurity in methanol is few, and quality is high, The volatile matter in low-order coal is substantially effectively utilized, and manufactures methanol feedstock and enriches, cost is relatively low, and life is greatly saved Cost, but also the rich upgraded coal and coal tar for producing high value are produced, state coal comprehensive utilization direction is met.

The above, the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although referring to before Stating embodiment, invention is explained in detail, those skilled in the art should understand that: it still can be to preceding Technical solution documented by each embodiment is stated to modify or equivalent replacement of some of the technical features；And these It modifies or replaces, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.

Claims

1. a kind of method for preparing methanol using volatile matter in low-order coal, it is characterised in that: comprise the following steps that:

(1) low-order coal passes sequentially through stoving process and gasification reducing process handles to obtain rich gas, and the rich gas passes through purification process Rich gas after being purified, the purified rich gas include CO, CO₂、H₂And hydro carbons, the gasification reducing process is in anaerobic Or the chemical reaction process that the low-order coal after drying is heated under micro-oxygen conditions；

(2) purified rich gas described in step (1) passes sequentially through sulfur removal technology and the first compression process handles to obtain reformation turn Change unstripped gas；

(3) reforming unstripped gas described in step (2) is obtained by reforming process comprising CO, CO₂And H₂Reformation Convert gas；

(4) reforming gas described in step (3) passes through in decarburization mend carbon technology, shift conversion technique and benefit hydrogen technique One or more obtain methyl methanol syngas, and the hydrogen-carbon ratio R value of the methyl methanol syngas is 2.05~2.1；

(5) methyl methanol syngas described in step (4) passes sequentially through the second compression process, methanol synthesizing process obtains crude carbinol and first Alcohol periodic off-gases, the crude carbinol pass through methanol rectification technique again and obtain product methanol.

2. a kind of method for preparing methanol using volatile matter in low-order coal as described in claim 1, it is characterised in that: step (2) sulfur removal technology described in includes fine desulfurizing technology and thick sulfur removal technology, and the purified rich gas passes sequentially through thick desulfurization work Skill, the first compression process and fine desulfurizing technology handle to obtain reforming unstripped gas.

3. a kind of method for preparing methanol using volatile matter in low-order coal as described in claim 1, it is characterised in that: step (4) reforming gas described in first passes through shift conversion technique and obtains conversion gas, and the conversion gas mends carbon by the decarburization again Technique obtains methyl methanol syngas.

4. a kind of method for preparing methanol using volatile matter in low-order coal as described in claim 1, it is characterised in that: step (4) decarburization mend carbon technology described in is to be passed through CO when the hydrogen-carbon ratio R value of the reforming gas is greater than 2.1₂, so that R value tune It is whole to 2.05-2.1；When the hydrogen-carbon ratio R value of the reforming gas is less than 2.05, CO is removed₂, so that R value is adjusted to 2.05- 2.1。

5. a kind of method for preparing methanol using volatile matter in low-order coal as claimed in claim 3, it is characterised in that: the change Change conversion process be during reforming unstripped gas to methyl methanol syngas by CO by with H₂O response transform is converted into H₂。

6. a kind of method for preparing methanol using volatile matter in low-order coal as described in claim 1, it is characterised in that: step (4) benefit hydrogen technique described in is that H is added during reforming gas to methyl methanol syngas₂Technique.

7. a kind of method for preparing methanol using volatile matter in low-order coal as described in claim 1, it is characterised in that: step (1) purification process described in includes dust collecting process and detar technique.

8. a kind of method for preparing methanol using volatile matter in low-order coal as described in claim 1, it is characterised in that: step (1) reaction temperature of gasification reducing process described in is 350-800 DEG C.

9. a kind of method for preparing methanol using volatile matter in low-order coal as described in claim 1, it is characterised in that: step (3) reforming unstripped gas described in through reforming process be reforming unstripped gas in gas each component without point From directly that some hydrocarbon in the reforming unstripped gas is reforming for CO and H₂Reforming technique.

10. a kind of method for preparing methanol using volatile matter in low-order coal as claimed in claim 9, it is characterised in that: described Reforming technique is converted selected from steam reformation, steam pure oxygen is reforming and pure oxygen is reforming one such or several.

11. a kind of method for preparing methanol using volatile matter in low-order coal as described in claim 1, it is characterised in that: step (2) pressure of the first compression process described in is 20-25kg, and temperature is 300-400 DEG C.

12. a kind of method for preparing methanol using volatile matter in low-order coal as described in claim 1, it is characterised in that: step (5) the pressure 40-50kg of the second compression process described in, temperature are 200-350 DEG C.