CN107400041A - The method that methanol and dimethyl ether processed are converted with calcium carbide stove exhaust resistant to sulfur isothermal - Google Patents

The method that methanol and dimethyl ether processed are converted with calcium carbide stove exhaust resistant to sulfur isothermal Download PDF

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Publication number
CN107400041A
CN107400041A CN201610335288.7A CN201610335288A CN107400041A CN 107400041 A CN107400041 A CN 107400041A CN 201610335288 A CN201610335288 A CN 201610335288A CN 107400041 A CN107400041 A CN 107400041A
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gas
calcium carbide
methanol
dimethyl ether
sulfur
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孙孟君
孙俊超
李君炎
何平元
廖绍元
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Maoxian Xinxin Energy Co Ltd
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Maoxian Xinxin Energy Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Abstract

A kind of method that methanol and dimethyl ether processed are converted with calcium carbide stove exhaust resistant to sulfur isothermal of the present invention, mainly by following steps：Pressurization steps, resistant to sulfur isothermal shift step, temp.-changing adsorption purifying step, pressure swing adsorption purge step, compression step, synthesizing methanol and dimethyl ether step, synthesis periodic off-gases carry hydrogen step and exhaust gas polishing steps；Improved technology, make production system operating flexibility bigger, in the case where whetheing there is sodium chlorate tail gas can balanced production, can be by calcium carbide stove exhaust all of both increasing yield, and do not put day lamp pollution environment.By reducing wet desulphurization, dry desulfurization, deoxidation, dearsenification process, the energy loss in gas course of conveying is reduced.It is exactly to increase the hydrogen psa rate of recovery in addition, reaches energy-conservation purpose.The improved technology is advanced, substantially reduces technological process, and Whole Process control is realized in operation, reduces human operational error.

Description

The method that methanol and dimethyl ether processed are converted with calcium carbide stove exhaust resistant to sulfur isothermal
Technical field
The present invention relates to Organic Chemicals manufacturing technology field, more particularly to one kind to convert methanol processed with calcium carbide stove exhaust resistant to sulfur isothermal With the method for dimethyl ether.
Background technology
For caused calcium carbide stove exhaust more than 15,000,000,000 mark sides, the overwhelming majority be vented or " point day lamp ", annual therefore suitable every year in China In 2,400,000 tons of standard coals of loss.12,000,000 tons of CO are discharged simultaneously2With 1,000,000 tons of dust.Very big environmental pollution is not only caused, more Cause the significant wastage of recoverable resource.For Economic Development Mode Conversion, country has put into effect target for energy-saving and emission-reduction, while various regions Specific emission reduction index is assigned by government.Calcium carbide stove exhaust complicated component, it is as shown in the table：
Calcium carbide tail gas main component：
Project CO H2 CO2 O2 N2 CH4
Content (V%) 74% 5% 14% 0.8% 6% 0.1%
Calcium carbide tail gas harmful substance：
Conversion outlet harmful substance：
Numerous ground harmful components in calcium carbide stove exhaust are removed, further separate CO therein2、CH4、H2Etc. component, difficulty is very Greatly, under prior art conditions, process route is grown, and investment is big, and operating cost is high, also can without the process route and technology of maturation It is selective.The raw material of the Chemical Manufacture of catalyst is used especially as methanol and dimethyl ether, even if micro impurity, it is also possible to cause Catalyst poisoning, cause production not carry out, or greatly increase operating cost, lose more than gain, therefore, the purification of calcium carbide stove exhaust Turn into the maximum technology barrier of industrial applications with high CO technologies are converted.
Domestic calcium carbide stove exhaust methanol has a Patents, Patent No. ZL200510085638.0, and the patent content includes profit Methanol is produced with calcium carbide stove exhaust or synthesizes the content of ammonia, but the purification method of calcium carbide stove exhaust is only disclosed after washing dedusting directly Into synthesis ammonia or system for methanol synthesis production synthesis ammonia or methanol.In fact, about more than 20 kind impurity are impossible in calcium carbide stove exhaust By a water-washing step with regard to the purification requirement of synthesizing methanol can be reached.Therefore, this patent is merely resting in theory, and real Apply, the purification techniques for not solving calcium carbide stove exhaust is impossible.There is one in addition and utilize calcium carbide stove exhaust and sodium chlorate tail gas The patent of methanol and dimethyl ether processed, though the patent can be applied, calcium carbide stove exhaust and sodium chlorate tail gas must match, if once chlorine Sour sodium tail gas supply goes wrong, then can not maintain to produce.And the application of calcium carbide stove exhaust isothermal converter technique, then tolerance it can become entirely Calcium carbide stove exhaust is changed, maintains normal production.
H2It is the unstripped gas of methanol processed with CO.As shown in figure 1, existing methanol processed and dimethyl ether process, are by furnace of calcium carbide (main component is H for tail gas (main component is CO, content 72%-75%) and sodium chlorate tail gas2, content 98%) purified treatment. Calcium carbide tail gas out-of-bounds enters gas holder buffer storage, and tail gas goes out gas holder and enters wet method crude desulphurization system after roots blower is pressurized.Thick desulfurization Using PDS aqueous slkalis, sulfur removing pregnant solution uses jet regeneration, removes the calcium carbide tail gas after H2S and goes to compress.The present apparatus sets three kinds of pressures Contracting machine：Calcium carbide tail gas compressor, hydrogen gas compressor and synthesis gas joint compressor.
Hydrogen after out-of-bounds purifying enters hydrogen gas holder, and after hydrogen gas compressor is pressurized, fraction enters conversion, largely goes joint to compress Machine.Calcium carbide tail gas goes smart purification through three stage compression to 1.5MPa, through temp.-changing adsorption, pressure-variable adsorption, fine desulfurization process by dry, deoxidation, reaches Go to compress after to desired impurity content, be compressed to 3.0-5.4MPa and go to synthesize.
In order to meet in Production of methanol to synthesis gas CO2The requirement of content, a by-pass is set, on a small quantity after purified treatment Calcium carbide tail gas enters a transformation system, and the CO in the part calcium carbide tail gas is transformed into CO again2, the gas after the conversion is through dividing From after cooling joint compressor is removed with main gas mixing.
Methanol purge gas reclaims hydrogen through pressure-swing absorption apparatus, and return system makees raw material.Putting forward hydrogenolysis air-breathing goes temp.-changing adsorption to do regeneration gas.
Synthesis gas, through catalyzing and synthesizing gaseous mixture containing methanol, isolates crude carbinol after heat exchange cools down, goes rectifying or go two in synthetic tower Methyl ether synthesis, rectifying.
Crude carbinol removes light component, pressurizing tower and atmospheric tower rectifying through pre-distillation column, and refined methanol is obtained from pressurizing tower and normal pressure column overhead Product, thermal source of the pressurizing tower overhead vapours as atmospheric tower reboiler.Analyze qualified refined methanol and go to tank field.
Crude carbinol also can directly go DME synthesis to produce dimethyl ether.
Existing apparatus technology is mainly to caused hydrogeneous waste gas in the purified treatment and production process of calcium carbide stove exhaust and sodium chlorate tail gas Recycling, and unnecessary calcium carbide stove exhaust is then used as the unstripped gas of synthesizing methanol by non-sulphur-resistant conversion hydrogen making, reaches and is System balance.By this technology, the comprehensive utilization to two kinds of tail gas, energy-saving and emission-reduction are realized.
Original process technology scheme, it is primarily present three defects.
First, existing apparatus technology, it is to be designed in the state of calcium carbide stove exhaust and the supply of sodium chlorate tail gas are more satisfactory, if chlorine Sour sodium tail gas supply deficiency, then occur that production system is unbalance, unnecessary calcium carbide stove exhaust can be then vented.In extreme circumstances, chlorine There is cut-off in sour sodium tail gas, and whole production system can not produce, then calcium carbide stove exhaust then all " point day lamp ", pollutes environment, together When also result in the loss of calcium carbide stove exhaust resource.
2nd, the non-sulphur-resistant conversion designed for matching production system, sulfur content must be controlled in the range of 0.1mg/L, otherwise can be right Transformation catalyst impacts, or even loses activity and scrap.Therefore wet method and dry method two-step desulfurization are devised, it is ensured that index meets It is required that.Both increase energy resource consumption, increase operating process and manipulation strength again.
3rd, hydrogen technology is carried by pressure-variable adsorption, recovery synthesizes the hydrogen of levels of hydrogen 40% or so in periodic off-gases (dropping a hint), the rate of recovery 70%-75%.Because the rate of recovery is relatively low, it is necessary to which multiple circulation and stress, increases energy consumption.
The content of the invention
It is an object of the invention to provide a kind of method that methanol and dimethyl ether processed are converted with calcium carbide stove exhaust resistant to sulfur isothermal, overcome with this The problems such as energy resource consumption in conventional method is high, processing step is complicated, operating flexibility is small and manipulation strength is big.
A kind of method that methanol and dimethyl ether processed are converted with calcium carbide stove exhaust resistant to sulfur isothermal of the present invention, its key step include：It is a kind of with The method that calcium carbide stove exhaust resistant to sulfur isothermal converts methanol and dimethyl ether processed, it is characterised in that：Comprise the following steps：
Wash dust removal step, pressurization steps, resistant to sulfur isothermal shift step, temp.-changing adsorption purifying step, pressure swing adsorption purge step, Compression step, synthesizing methanol and dimethyl ether step and exhaust gas polishing steps；
1) dust removal step is washed：Calcium carbide stove exhaust removes the dust in calcium carbide stove exhaust through spray washing.
2) pressurization steps：Through being forced into 1.5MPa after calcium carbide stove exhaust dedusting, and it is cooled to less than 40 DEG C；
3) resistant to sulfur isothermal shift step：
A. pressurization steps 2 will be passed through) high concentration CO gas content in 72%-75%, be introduced into the first purification furnace except deoiling and powder Dirt, enter back into the second purification furnace dephosphorization and defluorinate；
B. the gas Jing Guo a steps carries out heat exchange, and is heated to 180~200 DEG C, while supplements CS2, a small amount of water vapour Enter deoxygenation stove by electric heater afterwards, be equipped with what the impurity removal being harmful in calcium carbide tail gas to catalyst can be fallen in deoxygenation stove epimere Oxygen scavenger and Hydrodearsenic Catalyst；
C. the gas heating Jing Guo b step is gone forward side by side to 220 DEG C becomes owner of change furnace progress transformationreation, the gas of primary transform outlet of still Temperature is 210 DEG C -230 DEG C, wherein regulation conversion exports CO contents to 24-26%；
D. the gas Jing Guo step c continues transformationreation into deoxygenation stove hypomere, and deoxygenation stove hypomere outlet temperature is adjusted to 275-280 DEG C, the CO contents control 18%-20% in exit gas, temperature is then reduced to about 175 DEG C -180 DEG C, by desalted water Preheater heats desalted water；
E. less than 40 DEG C are cooled in water cooler by Step d conversion gas.
4) the temp.-changing adsorption purifying step：Cyanide in conversion gas of the removing Jing Guo step 3), phosphide, nitrogen at normal temperatures Oxide, impurity are made by adsorbed agent selective absorption, H2, O2, N2, CH4, CO, CO2 by bed at the top of absorber For preliminary clearning pneumatic transmission to next step；Rinse needed for temp.-changing adsorption regeneration gas from methanol-fueled CLC periodic off-gases carry hydrogen after resolution gas；
5) pressure swing adsorption purge step：Adsorbance is smaller in the calcium carbide tail gas Jing Guo step 4) temp.-changing adsorption purifying step at normal temperatures Weakly adsorbed components H2、O2、N2、CH4、CO、CO2Exported by adsorbent bed, the larger absorption by force of adsorbance is miscellaneous in calcium carbide tail gas Matter component phosphorus, arsenic, fluorine are adsorbed to stay in bed, and then decompression evacuates and the impurity desorption in retention bed is come out；
6) compression step：Calcium carbide stove exhaust by step 5) pressure swing adsorption purge step is first pressurized to synthesizing methanol before the synthesis Pressure index 3.0-5.3MPa；
7) synthesizing methanol and dimethyl ether step：Including crude carbinol synthesis step, rectification step and DME synthesis and rectification step；Through Calcium carbide stove exhaust CO, H of overcompression step 6)2And CO2Unstripped gas, in synthetic tower and in the presence of catalyst, generate thick first Alcohol gas, by obtaining crude carbinol after cooling, crude carbinol purification is by pre-distillation column, atmospheric tower and pressurizing tower, obtains refined methanol；
Crude carbinol dimethyl ether synthesis is further dehydrated by evaporator, gasification tower, DME synthesis tower, obtains dimethyl ether；
8) exhaust gas polishing steps：The flash steam after resolution gas, synthetic coarse methanol by temp.-changing adsorption purifying step enters waste gas Boiler combustion, flue gas caused by burning discharge after processing is up to standard.
Further, in step 3), the deoxygenation furnace interior is provided with the water spray cold shock device for cooling；Primary transform stove uses temperature control Shift-converter, and its inlet temperature is adjusted by injection flow rate.
Further, it is to control CO by adjusting steam addition CO contents to be adjusted in the step c of the step 3) to 24-26% Content.
Further, regulation requires the μ S/cm of the electrical conductivity of desalted water≤1 in the step d of the step 3).
Further, be additionally provided with blend step between the pressure swing adsorption purge step and compression step, in the blend step and Pressure-variable adsorption is additionally provided between crude carbinol synthesis step and puies forward hydrogen step；
The blend step refers to that the calcium carbide tail gas after pressure swing adsorption purge step process, synthesis periodic off-gases carry hydrogen through pressure-variable adsorption Step carry the hydrogen after hydrogen, it is purified after the obtained H of gas shift reaction2Mixing, hydrocarbon mixing ratio is 2-2.5；The transformation is inhaled The attached hydrogen step that carries refers to that unreacted hydrogen is separated from separator in crude carbinol building-up process, and methanol purge gas passes through the step Reclaim H therein2, the H2Return to blend step to be mixed, carry the stripping gas after hydrogen and enter back into temp.-changing adsorption process as flushing gas.
Further, gaseous mixture forms in the blend step：CO is 27%, CO2For 2.5%, H2For 66%, CH4For 0.35%, N and Ar is 4.05%, O2For O.05%, remaining impurity content≤0.1ppm.
Further, in the pressure-variable adsorption puies forward hydrogen step, the stripping gas that methanol purge gas carries hydrogen production device is used as temp.-changing adsorption cold blowing gas. Cold blowing gas, which enters absorber, reduces absorber temperature with adsorbing contaminant, heats rinsing desorption, regeneration off gases enter waste gas through waste gas header Processing system.
Further, the pressurization steps 2) a portion gas enters the temp.-changing adsorption purifying step removal of impurity.
Further, the pressurization steps 2) in be forced into 1.5MPa be to first pass through water ring compressor to be pressurized to 50KPa, then to calcium carbide Tail-gas compressor is pressurized to 1.5MPa；Compression step 6) in calcium carbide stove exhaust be first pressurized to 1.5MPa before the synthesis, repressurization arrives 5.4MPa。
Further, the temp.-changing adsorption purifying step 4) in temperature operating ranges be 5-40 DEG C；It is preferred that 25-35 DEG C；The transformation is inhaled Attached purifying step 5) pressure operation scope is 0.5-2.OMPa, preferably 1.0-1.5MPa；Synthetic tower in the crude carbinol synthesis step Temperature operating ranges are 190-260 DEG C, preferably 190-210 DEG C.
By a kind of method that methanol and dimethyl ether processed are converted with calcium carbide stove exhaust resistant to sulfur isothermal of the present invention, using the technique after improvement Technology, reach volume increase, energy-conservation, simplification of flowsheet and the technique effect for simplifying operation.
(1) improved technology, make production system operating flexibility bigger, the energy balanced production in the case where whetheing there is sodium chlorate tail gas, Can be by calcium carbide stove exhaust all of both increasing yield, and do not put day lamp pollution environment.
(2) by reducing wet desulphurization, dry desulfurization, deoxidation, dearsenification process, the energy loss in gas course of conveying is reduced.In addition It is the increase hydrogen psa rate of recovery, reaches energy-conservation purpose.
(3) the improved technology is advanced, substantially reduces technological process, and Whole Process control is realized in operation, reduces human operational error.
Brief description of the drawings
Accompanying drawing 1 is that existing calcium carbide tail gas purifies methanol and dimethyl ether flow chart processed；
Accompanying drawing 2 purifies methanol and dimethyl ether flow chart processed for the calcium carbide tail gas of the present invention.
Embodiment
The content of the invention of the present invention is described in further detail with reference to embodiment.It should be understood that the implementation of the present invention Example is served only for illustrating the present invention without limiting the present invention, in the case where not departing from the technology of the present invention thought, according to the common skill in this area Art knowledge and customary means, the various replacements and change made, all should be included within the scope of the invention.
Below by specific embodiment, the present invention will be further described
Its key step includes：Water ring pump and compressor pressurization steps, temp.-changing adsorption purification, pressure swing adsorption purge, H2With CO gases Mixing, synthetic coarse methanol, crude carbinol purification, crude carbinol dimethyl ether synthesis, synthesis periodic off-gases put forward hydrogen, exhaust-gas treatment in proportion.
Temp.-changing adsorption step is to remove cyanide, phosphide, the nitrogen oxides in calcium carbide tail gas, and impurity passes through adsorbed agent selectivity Absorption, H2、O2、N2、CH4、CO、CO2Preliminary clearning pneumatic transmission is used as to pressure-variable adsorption step at the top of absorber by bed.Temperature Opereating specification is 5-40 DEG C, preferably 25-35 DEG C.
Pressure-variable adsorption step is the less weakly adsorbed components H of adsorbance in calcium carbide tail gas2、O2、N2、CH4、CO、CO2Pass through adsorbent Bed output, the larger strong adsorbing contaminant component phosphorus of adsorbance, arsenic, fluorine are adsorbed in calcium carbide tail gas stays in bed, and then decompression is staying The impurity desorption deposited in bed comes out.Pressure operation scope is 0.5-2.OMPa, preferably 1.0-1.5MPa.
Blend step is hydrogen after carrying hydrogen of calcium carbide tail gas after purified processing, synthesis periodic off-gases, it is purified after go conversion after obtain H2Mixing.Hydrogen carbon mixing ratio is 2-2.5.
Compression step be calcium carbide stove exhaust before cleaning by being pressurized to 1.5MPa, reach defined pressure index.It is synthesis gas in addition By being pressurized to 5.4MPa, reach the pressure index of synthesizing methanol.
Synthesizing methanol is CO, H2And CO2Unstripped gas, temperature is about generation in the presence of 190-210 DEG C and catalyst in synthetic tower Crude carbinol gas, by obtaining crude carbinol, content about 95% after cooling.
Crude carbinol purification is by pre-distillation column, atmospheric tower and pressurizing tower, obtains refined methanol, content 99.9%.
Crude carbinol dimethyl ether synthesis is further dehydrated by reboiler, DME synthesis tower, obtains dimethyl ether, content 99.9%.
It is that unreacted gas is sent out from separator in Production of methanol that synthesis periodic off-gases, which carry hydrogen, unreacting gas (methanol purge gas) Hydrogen production device is carried by pressure-variable adsorption and reclaims H therein2.The H2Return to synthesis system and continue to participate in reaction.The stripping gas after hydrogen is carried to be used as Temp.-changing adsorption regeneration gas.Methanol purge gas carries the stripping gas of hydrogen production device and first passes through cold blowing step absorber in the step, and cold blowing waste gas is again Enter heating stepses absorber after heat exchanger heats up, heat rinsing desorption to the impurity on adsorbent, regeneration off gases are total through waste gas Pipe enters exhaust treatment system.
Exhaust-gas treatment is that total system collection combustible exhaust gas goes three wastes boiler combustion, and production steam uses for production system.Caused by burning Flue gas qualified discharge after processing.
The defects of to overcome prior art to exist, to realize under the conditions of without sodium chlorate tail gas, by carrying out resistant to sulfur to calcium carbide stove exhaust Isothermal low-temperature converts, and obtains CO2With unstripped gas H2, unnecessary CO2Removed, another step purification, obtained by converting pressure adsorption technology 99.9% technical grade CO2Product.The advanced technology, existing wet method and dry method two-step desulfurization are deleted, and reduce technological process. (see the process chart of accompanying drawing 1,2 before and after improvement)
In addition, carrying out technology upgrading to existing pressure swing adsorption, by intensified pressure, change the measures such as sequential, realize disposable H2Yield reaches more than 95%, reaches the purpose for not only saving but also increasing production.
As shown in Figure 2, calcium carbide stove exhaust out-of-bounds, is used after bag-type dustBlower fanConvey into gas holder buffer storage, temperature≤40 DEG C, Pressure 4-6KPa, tail gas go out gas holder after water ring compressor is pressurized to 0.5MPa, then are pressurized to 1.5MPa to calcium carbide tail gas compressor Afterwards, a part of gas is sent to the conversion of resistant to sulfur isothermal, and another part gas is directly sent to temp.-changing adsorption removal of impurity component.
The temperature shift reactions such as resistant to sulfur：It is net that the calcium carbide stove exhaust (temperature≤40 DEG C, pressure 1.5MPa) come from compressor is introduced into first Change stove oil removing and dust；Subsequently into the second purification furnace dephosphorization, defluorinate (oil removing, dechlorination are placed before compression), hot friendship is entered back into, Calcium carbide stove exhaust is heated to 180~200 DEG C of supplement CS2, with removing deoxygenation stove by electric heater after a small amount of steam.In deoxygenation stove epimere Equipped with oxygen scavenger and Hydrodearsenic Catalyst, the impurity removal being harmful in calcium carbide tail gas to catalyst can be fallen.Afterwards, calcium carbide tail gas spray cooling Enter primary transform stove (temperature control change furnace) to 220 DEG C and carry out transformationreation.
About 230 DEG C of primary transform outlet of still conversion gas temperature, the control of CO contents is 26% (butt vol, by adjusting steaming in process gas Vapour addition controls CO contents), add and continue transformationreation into deoxygenation stove hypomere after steam.
The outlet of deoxygenation stove hypomere meets that the control of CO contents is given for about 280 DEG C for 19.4% (meeting methanol-fueled CLC needs) temperature into heat The calcium carbide stove exhaust heat exchange of this process, the temperature of conversion process gas are down to 180 DEG C, heat desalted water by desalination water preheater, finally Cool down Qu Xia workshop sections.
2.0MPa steam caused by temperature control shift-converter drum is applied to this workshop section.Cold desalted water is sent after the heating of desalination water preheater To low pressure oxygen-eliminating device.
The total WGR of the program is 0.46.Hydrogen sulfide content in conversion gas is needed to reach 120mg/Nm3.By calcium carbide stove exhaust amount 10000Nm3/h is calculated, then needs to supplement H2S1.7kg/h (equivalent CS2 is 1.95kg/h).
The shortcomings that throughput that isothermal conversion effectively overcomes conventional transformation is small, and steam economy is big, and operation and maintenance cost are high, it is real Show beds isothermal operation, extend catalyst service life.
The design is 10000Nm3The CO Varying Process of/h calcium carbide tail gas device for producing hydrogen, in order to improve in unstripped gas Hydrogen content, reduce carbon monoxide content therein.
Carbon monoxide and vapor react generation carbon dioxide and hydrogen in the presence of catalyst.Its reaction equation：
CO+H2O=CO2+H2+410894kJ/kmol
Referred to as gas shift reaction, abbreviation transformationreation.
Transformationreation is heat release equimolecular reversible reaction.Therefore CO in conversion gas can all be reduced by reducing reaction temperature and increase steam consumption Equilibrium concentration, if temperature is high, quantity of steam is few, will be unfavorable for reacting condition even it may also happen that reverse shift reaction process.Wanting Ask under conditions of CO concentration is certain in conversion gas, it is to reduce the necessary means of steam consumption to reduce reaction temperature.Reaction can not reduced Under temperature conditionss, coveting reduces CO concentration, it will causes great waste of steam.
The process description of resistant to sulfur isothermal shift-reaction step：The calcium carbide tail gas of compressor outlet enter system before should be cooled to 40 DEG C with Under, it just can guarantee that oil expeller separates most oil.Oil expeller hypomere silk screen should be rinsed regularly.Degreaser is used to further inhale The oil and dust of attached calcium carbide tail gas, in order to avoid occluding device, pollution catalyst.Second purification furnace fills defluorinating agent and Hydrodearsenic Catalyst to remove original Expect fluorine, the noxious material such as phosphorus, (arsenic is on deoxygenation stove upper strata) in gas.Degreaser needs to regularly replace.
What main heat was handed over is heated to calcium carbide tail gas 200 DEG C, and the by-pass of setting has self-adjusting valve, available for automatically controlling deoxygenation stove entrance temperature Degree.Another effect of cold by-pass is to be used for rapid cooling when oxygen content runs high.
The setting of deoxygenation stove considers the influence of the changeable catalyst changeout of fluctuation of oxygen content in calcium carbide furnace gas, and inside sets water spray cold shock device With cooling.
Primary transform stove uses temperature control shift-converter, by controlling drum byproduct steam pressure effectively to control catalyst bed reaction Temperature, the problem of reaction temperature for avoiding high CO from bringing is too high.Primary transform stove inlet temperature is adjusted with injection flow rate.
Desalination water quality for humidification is very crucial, because injection flow rate is larger, even if containing a small amount of salt in desalted water, day accumulates the moon It is tired to will also result in substantial amounts of salt absorption in beds, increase catalyst bed layer resistance, activity decrease.It is required that desalination water quality The μ S/cm of electrical conductivity≤1.
When adjusting charging temperature with amount of humidification, to avoid humidification band water, not preferably less than 200 DEG C of inlet temperature.
Temp.-elevating electric furnace is placed in system, is easy to out, is stopped and elevated temperature cure.
Gas after isothermal conversion, 40 DEG C, pressure 1.3-1.5MPa of temperature remove 6 temperature-change adsorption towers, and removing is fallen miscellaneous in gas Matter component.Most impurity component is by TSA adsorbent selective absorptions, H in calcium carbide stove exhaust2、O2、N2、CH4、CO、CO2 Deng then by bed from being used as preliminary clearning pneumatic transmission to PSA at the top of absorber.Remaining five tower carries out other step operations respectively, and 6 towers are handed over For switching.Calcium carbide stove exhaust continuously inputs, TSA purification continuous-stable outputs.The purified gas that tower top comes out delivers to PSA.Absorption is being inhaled Impurity on attached dose carries the stripping gas of hydrogen from methanol purge gas, first passes through cold blowing absorber by heating rinsing desorption, regeneration gas, Heated device is warming up to 230 DEG C of entrance heating stepses absorbers to cold blowing waste gas again, and regeneration off gases go to handle through waste gas header.
Gas falls unnecessary CO to 10 pressure-swing absorbers, removing again after temp.-changing adsorption2Gas, pressure about 1.5MPa, 40 DEG C of temperature. Gas initially enters the pressure-swing absorber for being in adsorbed state, and impurity is adsorbed by PSA adsorbents, and weakly adsorbed components then pass through bed Exported as product gas.Remaining 8 tower alternating handover operation.TSA, the stripping gas of PSA system inverse put discharge go exhaust-gas treatment.Should Process produces reverse gas and returns to Water-ring vacuum pump inlet, reuses.
Gas after pressure-variable adsorption is sent to blender by synthesizing methanol C/Hratio requirement, while after methanol purge gas Pressure Swing Adsorption Hydrogen also add in gaseous mixture, form synthesis gas, three kinds of gases are pressurized to 5.4MPa by combining compressor and remove methanol-fueled CLC.It is mixed Close gas composition：CO27%, CO22.5%th, H66%, CH4O.35%, N+Ar4.05%, O20.05%, remaining impurity content≤0.1ppm.
Synthesis gas in synthetic tower through catalyzing and synthesizing gaseous mixture containing methanol, temperature control 210~260 DEG C, Stress control 3.0~ 5.4MPa, crude carbinol is isolated after changing cooling, crude carbinol, which removes, contains methanol, water and a small amount of ethanol, methyl formate, dimethyl ether Outside Deng organic impurities, a small amount of unreacting gas are dissolved (wherein with CO wherein also having2Content is most), the big portion of gas of these dissolvings After lease making vacuum flashing removing, crude carbinol sends to methanol rectification process.Most of unreacting gas continue cycling through use, and will be a small amount of Gas discharges, with the content of inert gas in control system.Crude carbinol removes light component through pre-distillation column, then goes pressurizing tower and normal pressure Tower rectifying, refined methanol product is obtained from pressurizing tower and normal pressure column overhead.Crude carbinol also can directly go DME synthesis, rectifying, produce Dimethyl ether.
Methanol purge gas reclaims hydrogen through pressure-swing absorption apparatus, returns to blender and makees raw material.Put forward hydrogenolysis air-breathing and go temp.-changing adsorption to do and regenerate Gas.
The flash steam after resolution gas, synthesis after temp.-changing adsorption goes three wastes boiler combustion, and production steam uses for production system.

Claims (10)

  1. A kind of 1. method that methanol and dimethyl ether processed are converted with calcium carbide stove exhaust resistant to sulfur isothermal, it is characterised in that：Comprise the following steps：
    Water-washing step, pressurization steps, resistant to sulfur isothermal shift step, temp.-changing adsorption purifying step, pressure swing adsorption purge step, pressure Contracting step, synthesizing methanol and dimethyl ether step and exhaust gas polishing steps；
    1) water-washing step：Calcium carbide stove exhaust removes the dust in calcium carbide stove exhaust through spray washing；
    2) pressurization steps：Through being forced into 1.5MPa after calcium carbide stove exhaust dedusting, and it is cooled to less than 40 DEG C；
    3) resistant to sulfur isothermal shift step：
    A. pressurization steps 2 will be passed through) high concentration CO gas content in 72%-75%, be introduced into the first purification furnace except deoiling and Dust, enter back into the second purification furnace dephosphorization and defluorinate；
    B. the gas Jing Guo a steps carries out heat exchange, and is heated to 180~200 DEG C, while supplements CS2, after water vapour Enter deoxygenation stove by electric heater, be equipped with what the impurity removal being harmful in calcium carbide tail gas to catalyst can be fallen in deoxygenation stove epimere Oxygen scavenger and Hydrodearsenic Catalyst；
    C. the gas heating Jing Guo b step is gone forward side by side to 220 DEG C becomes owner of change furnace progress transformationreation, the gas of primary transform outlet of still Temperature is 210 DEG C -230 DEG C, wherein adjusting CO contents to 24%-26%；
    D. the gas Jing Guo step c continues transformationreation into deoxygenation stove hypomere, and deoxygenation stove hypomere outlet temperature is adjusted to 275-285 DEG C, the CO contents control 18%-20% in exit gas, temperature is then reduced to 175 DEG C -185 DEG C, by desalted water Preheater heats desalted water；
    E. cooler built in inside is cooled to less than 40 DEG C；
    4) the temp.-changing adsorption purifying step：At normal temperatures the cyanide in calcium carbide tail gas of the removing Jing Guo step 3), phosphide, Nitrogen oxides, impurity pass through adsorbed agent selective absorption, H2、O2、N2、CH4、CO、CO2By bed at the top of absorber As preliminary clearning pneumatic transmission to next step；
    5) pressure swing adsorption purge step：At normal temperatures in the calcium carbide tail gas Jing Guo step 4) temp.-changing adsorption purifying step adsorbance compared with Small weakly adsorbed components H2、O2、N2、CH4、CO、CO2Exported by adsorbent bed, the larger strong suction of adsorbance in calcium carbide tail gas Attached impurity composition phosphorus, arsenic, fluorine are adsorbed to stay in bed, and then decompression evacuates and the impurity desorption in retention bed is come out；
    6) compression step：Calcium carbide stove exhaust by step 5) pressure swing adsorption purge step is first pressurized to synthesis first before the synthesis The pressure index of alcohol；
    7) synthesizing methanol and dimethyl ether step：Including crude carbinol synthesis step, rectification step and DME synthesis and rectification step； By compression step 6) calcium carbide stove exhaust CO, H2And CO2Unstripped gas, in synthetic tower and in the presence of catalyst, generation Crude carbinol gas, by obtaining crude carbinol after cooling, crude carbinol purification is by pre-distillation column, atmospheric tower and pressurizing tower, obtains essence Methanol；
    Crude carbinol dimethyl ether synthesis is further dehydrated by evaporator, gasification tower, DME synthesis tower, obtains dimethyl ether；
    8) exhaust gas polishing steps：Flash steam after resolution gas, synthetic coarse methanol by temp.-changing adsorption purifying step enters useless Gas boiler burns, and flue gas caused by burning discharges after processing is up to standard.
  2. A kind of 2. method that methanol and dimethyl ether processed are converted with calcium carbide stove exhaust resistant to sulfur isothermal as claimed in claim 1, it is characterised in that： In step 3), the deoxygenation furnace interior is provided with the water spray cold shock device for cooling；Primary transform stove uses temperature control transformationreation Device, and its inlet temperature is adjusted by injection flow rate.
  3. A kind of 3. method that methanol and dimethyl ether processed are converted with calcium carbide stove exhaust resistant to sulfur isothermal as claimed in claim 1, it is characterised in that： It is to control CO contents by adjusting steam addition that CO contents are adjusted in the step c of the step 3) to 24-26%.
  4. A kind of 4. method that methanol and dimethyl ether processed are converted with calcium carbide stove exhaust resistant to sulfur isothermal as claimed in claim 1, it is characterised in that： Regulation requires the μ S/cm of the electrical conductivity of desalted water≤1 in the step d of the step 2).
  5. A kind of 5. method that methanol and dimethyl ether processed are converted with calcium carbide stove exhaust resistant to sulfur isothermal as claimed in claim 1, it is characterised in that： Blend step is additionally provided between the pressure swing adsorption purge step and compression step, is synthesized in the blend step and crude carbinol Pressure-variable adsorption is additionally provided between step and puies forward hydrogen step；
    The blend step refers to that the calcium carbide tail gas after pressure swing adsorption purge step process, synthesis periodic off-gases carry through pressure-variable adsorption Hydrogen step carry the hydrogen after hydrogen, it is purified after the obtained H of gas shift reaction2Mixing, hydrocarbon mixing ratio are 2~2.5；The change Pressure absorption puies forward hydrogen step and refers to that unreacted hydrogen is separated from separator in crude carbinol building-up process, and methanol purge gas passes through The step reclaims H therein2, the H2Return to blend step to be mixed, carry the stripping gas after hydrogen and enter back into temp.-changing adsorption purification step Rapid be used as rinses gas.
  6. A kind of 6. method that methanol and dimethyl ether processed are converted with calcium carbide stove exhaust resistant to sulfur isothermal as claimed in claim 5, it is characterised in that： Gaseous mixture forms in the blend step：CO is 27%, CO2For 2.5%, H2For 66%, CH4Be 4.05% for 0.35%, N and Ar, O2For 0.05%, remaining impurity content≤0.1ppm.
  7. A kind of 7. method that methanol and dimethyl ether processed are converted with calcium carbide stove exhaust resistant to sulfur isothermal as claimed in claim 5, it is characterised in that： In the pressure-variable adsorption puies forward hydrogen step, the stripping gas that methanol purge gas carries hydrogen production device is used as temp.-changing adsorption cold blowing gas, and cold blowing gas enters Entering temperature swing adsorbers reduces absorber temperature with adsorbing contaminant, heats rinsing desorption, regeneration off gases enter at waste gas through waste gas header Reason system.
  8. A kind of 8. method that methanol and dimethyl ether processed are converted with calcium carbide stove exhaust resistant to sulfur isothermal as claimed in claim 1, it is characterised in that： The pressurization steps 2) a portion gas enters the temp.-changing adsorption purifying step removal of impurity.
  9. 9. a kind of method that methanol and dimethyl ether processed are converted with calcium carbide stove exhaust resistant to sulfur isothermal as described in claim any one of 1-8, its It is characterised by：The pressurization steps 2) in be forced into 1.5MPa be to first pass through water ring compressor to be pressurized to 50KPa, then to calcium carbide Tail-gas compressor is pressurized to 1.5MPa；Compression step 6) in calcium carbide stove exhaust be first pressurized to 1.5MPa before the synthesis, repressurization arrives 5.4MPa。
  10. 10. a kind of method that methanol and dimethyl ether processed are converted with calcium carbide stove exhaust resistant to sulfur isothermal as described in claim any one of 1-8, its It is characterised by：The temp.-changing adsorption purifying step 4) in temperature operating ranges be 5~40 DEG C；It is preferred that 25-35 DEG C；The transformation Adsorption cleaning step 5) pressure operation scope is 0.5-2.0MPa, preferably 1.0-1.5MPa；In the crude carbinol synthesis step Synthetic tower temperature operating ranges are 190-260 DEG C, preferably 190-210 DEG C.
CN201610335288.7A 2016-05-20 2016-05-20 The method that methanol and dimethyl ether processed are converted with calcium carbide stove exhaust resistant to sulfur isothermal Pending CN107400041A (en)

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