CN108128776A - It is a kind of using coal bed gas as the method for Material synthesis carbon disulfide - Google Patents

It is a kind of using coal bed gas as the method for Material synthesis carbon disulfide Download PDF

Info

Publication number
CN108128776A
CN108128776A CN201710242801.2A CN201710242801A CN108128776A CN 108128776 A CN108128776 A CN 108128776A CN 201710242801 A CN201710242801 A CN 201710242801A CN 108128776 A CN108128776 A CN 108128776A
Authority
CN
China
Prior art keywords
carbon disulfide
gas
sulphur
liquid
enters
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201710242801.2A
Other languages
Chinese (zh)
Inventor
朱远斌
郭才才
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yangcheng County Ruixing Chemical Co Ltd
Original Assignee
Yangcheng County Ruixing Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yangcheng County Ruixing Chemical Co Ltd filed Critical Yangcheng County Ruixing Chemical Co Ltd
Priority to CN201710242801.2A priority Critical patent/CN108128776A/en
Publication of CN108128776A publication Critical patent/CN108128776A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Industrial Gases (AREA)

Abstract

One kind is using coal bed gas as Material synthesis CS2Method be related to a kind of productive method of chemical engineering.Method of the present invention using coal bed gas as Material synthesis carbon disulfide provides a kind of good operation safety, environmental-friendly, the higher CS of yield2Synthetic method, industrialized production and meet people to CS to realize2Demand, and in the fixed bed reactors that can be loaded in no catalyst, coal seam gas phase is made to carry out CS in the fixed bed reactors of two series connection2Synthesis；And can realize the recycling of sulphur and recycle, this Technical comparing is ripe, and economic benefit reaches maximization.

Description

It is a kind of using coal bed gas as the method for Material synthesis carbon disulfide
Technical field
The present invention relates to one kind using coal bed gas as Material synthesis CS2Method.
Background technology
Carbon disulfide is a kind of important industrial chemicals reacted at high temperature with sulphur steam by carbon containing matter, The production divisions such as staple fibre, glassine paper, pesticide, carbon tetrachloride, rubber, technics of metallurgy mineral dressing, petroleum refining and military project have extensively Using.With the rapid development of the industry such as China's chemistry, metallurgy, the purposes of carbon disulfide is more and more extensive.It is this in order to adapt to It needs, the carbon disulphide production in China is also evolving.
China's traditional mode of production carbon disulfide uses ancient electric furnace process, using charcoal and sulphur as raw material.This not only a large amount of consumption The forest reserves, and poisonous and hazardous H is generated in process of production2S gases, technique are ancient, backward, low production efficiency, condition Difference is unfavorable for environmental protection, belongs to the production line being eliminated.At present, charcoal is replaced to produce two sulphur using natural gas by raw material The method for changing carbon is that the advanced production line of first choice, foreign countries generally use the FMC skills of three kinds of technologies, the i.e. U.S. both at home and abroad at present Art (Food Machinary and Chemical Co.), Staufer technologies and PPG technologies, wherein FMC technologies are current days A kind of more advanced technology of right gas method production carbon disulfide.In addition with French Bu Luoji companies (Progil) using propylene as The production technology of raw material, it is superior with coal bed gas due to being not so good as using propylene as raw material, seldom use.But the high pressure used at present Catalysis, low-pressure catalytic processes technology, catalyst silica gel, activated alumina, diatomite, alumina glue, bauxite etc., temperature Range is at 500-700 DEG C, but flow should be particularly mentioned that raw material will be pre-processed using during catalyst, make C in coal bed gas3Hydrocarbon contains Amount must not exceed 4 %, C4Hydrocarbon content must not exceed 0.7%;The carbon-containing impurities of sulphur also have defined.It will if raw material is not met Ask, the polysulfides of generation can gather and cause catalyst " poisoning " on a catalyst, coking and blocking, prevent reaction from after It is continuous to carry out and more demanding to the methane molar concentration in coal bed gas.Therefore uncatalyzed reaction flow can avoid more than disadvantage, Raw material coal bed gas is required also to react stringent like that without catalysis, realizes and curing is produced with the uncatalyzed reaction of coal bed gas and sulphur Carbon, experimental study ensure the technology of serialization safety, so as to make system long time running, do not analyse carbon, noncoking is blocked up Plug, and obtain high conversion.But current high pressure non catalytic technique and low-pressure, non-catalytic technology, also all there is not Same exacting terms.Such as due to condensation effect difference, CS in fixed gas2Content raising, material is caused artificially to be lost in, product Yield declines and vent gas treatment all causes specific energy consumption height.Therefore to solve these problems, we are born using no catalyst The synthetic technology of load realizes CS2Synthesis be necessary.
Invention content
The defects of it is an object of the invention to overcome the prior art, provides a kind of good operation safety, environmental-friendly, yield Higher CS2Synthetic method, industrialized production and meet people to CS to realize2Demand, and can be loaded in no catalyst In fixed bed reactors, coal seam gas phase is made to carry out CS in the fixed bed reactors of two series connection2Synthesis；And it can realize sulphur It recycles and recycles, this Technical comparing is ripe, and economic benefit reaches maximumlly using coal bed gas as Material synthesis carbon disulfide Method.
It is of the present invention using coal bed gas as the method for Material synthesis carbon disulfide, be come real using following technical scheme It is existing：
One kind is using coal bed gas as Material synthesis CS2Method include the following steps：
（1）Solid sulfur is molten sulfur with steam indirectly heat by sulfur melting groove, and molten sulfur is entered filter by liquid sulfur pump, is passed through It obtains clarifying pure liquid sulfur after filter filtering, content 99.8% enters heating reaction furnace through the pressurization of sulphur metering pump；
（2）Molten sulfur is reacted with coal bed gas in heating reaction furnace to be generated carbon disulfide and hydrogen sulfide process gas and passes through reactor Further reaction；
（3）The complete sulphur condensation of unreacted is liquid, and into sulphur device is caught, the liquid sulfur after trapping is passed through is carried out boiling by sulphur device, Entered by the gaseous state carbon disulfide that the boiling of sulphur device comes out and catch sulphur device, liquid sulfur enters flash vessel, and liquid sulfur is in molten sulfur flash vessel Further boiling is carried out, gas enters water seal recycling carbon disulfide, and liquid sulfur is put into sulfur melting groove；
（4）It catches sulphur device Process Gas and enters carbon disulfide water condenser, gas is cold by carbon disulfide by carbon disulfide water condenser It coagulates for liquid, carbon disulfide water condenser gas enters carbon disulfide brine condenser, carries out further sub-cooled, by liquid Hydrogen sulfide detaches in carbon disulfide；
（5）Liquid carbon disulphide enters refining desulfurization tower, and gas enters hydrogen sulfide water cooling and vulcanization hydrogen salt is cold, passes through sub-cooled Afterwards, liquid carbon disulphide enters destilling tower, and destilling tower steams the incoagulable gas in carbon disulfide, and carbon disulfide liquid is by sulphur Enter reservoir area storage tank after changing hydrogen water cooling and the cold sub-cooled of salt；
（6）The cold middle hydrogen sulfide gas of carbon disulfide salt enters Crouse's hydrogen sulfide surge tank, enters back into the progress of Crouse's combustion furnace Combustion reaction Recovered sulphur, vulcanization hydrogen salt cold air enter water seal recycling carbon disulfide, and gas enters Crouse's incinerator through burning After burning, then take double calcium method desulfurization technologies generation calcium sulfate, i.e. gypsum, so as to fulfill sulphur recycling and recycle.
The above process may be used following chemical equations and represent：
In above-mentioned steps 1, the gaseous mixture that molar content is more than 96% in selection coal bed gas is according to the carbon and sulphur in the gaseous mixture The raw material proportioning that the molar ratio of sulphur is 1: 2-3 carries out dispensing.Theoretically sulfur consumption general excessive 5%, need to prevent methane hot tearing Solution generates carbon black, after dispensing is preheated to 300-500 DEG C in reacting furnace, under the conditions of gauge is 800-1000kPa.
In above-mentioned steps 2, coal bed gas carries out vulcanization reaction with Molten sulphur, and dynamics is carried out to carbon disulfide synthetic reaction Pre-test, this reaction are the endothermic reaction in low temperature, and are at high temperature exothermic reaction, about at 680 DEG C, the fuel factor of reaction It is zero.Temperature raising reaction speed is accelerated, and still, temperature is excessively high, will influence the boiler tube service life.In addition, it is to put that temperature, which is more than 680 DEG C, Thermal response continues to improve temperature, and equilibrium conversion can decrease.Therefore temperature control carries out anti-under the conditions of 650-700 DEG C Should, then whole process streams enter in adiabatic reactor, and reaction time is 5-10 seconds.
It, can be by the H of attached production by automatically controlling air dosage and reaction temperature in above-mentioned steps 62S is converted into sulphur, Double calcium method desulfurization technology generation calcium sulfate are taken again（Gypsum）, can toxic tail gas be converted with almost all, so as to fulfill returning for sulphur It receives and recycles.
The technical solution adopted by the present invention has the following advantages that compared with prior art:
1. the present invention will save a large amount of high-quality natural gases using coal bed gas, this keeps life to expanding carbon disulphide production raw material State balances, and environmental protection plays positive effect, while can also substantially reduce production cost, has significant social benefit and economy Benefit.
2. extensive carbon disulfide preparation facilities is susceptible to the influence of demand fluctuating, it can only be used>The height of 98 % The coal bed gas of purity methane must remove heavy paraffin hydrocarbon in coal bed gas, so as to increase investment of production and operating cost.The present invention We take high temperature to choose the gaseous mixture that molar content in coal bed gas is more than 96% without catalyst system and catalyzing and synthesized, expanded former Expect range.
3. vulcanization reaction does not use catalyst in the present invention, using high temperature without Catalytic processes, and in tail gas, using catalysis Processing has the advantages that price is low, and reaction efficiency height, floor space is small, low in the pollution of the environment.
4. final gas enters Crouse's incinerator through calcination in the present invention, it is smaller can toxicity to be converted into almost all SO2, then take double calcium method desulfurization technology generation calcium sulfate（Gypsum）, so as to fulfill sulphur recycling and recycle.
Specific implementation method：
Fig. 1 is the technological process diagram of the present invention:
In figure：1- sulfur melting grooves；2- heating reaction furnaces；3- condensers；4- catches sulphur device;5- is by sulphur device;6- flash vessels;7- condensers; 8- condensers;9- refining desulfurization towers;10- condensers；11- distillers；12- Crouse's combustion furnaces；13- exhaust treatment systems.
Specific embodiment
Knot contains specific example to technical scheme of the present invention further description below, but the present invention should not be limited only to this A bit.
Embodiment 1
It is a kind of using coal bed gas as the method for Material synthesis carbon disulfide, successively including six following steps:
（a）Solid sulfur passes through sulfur melting groove（1）It is molten sulfur with steam indirectly heat, molten sulfur is pumped by filter by liquid sulfur pump, It obtains clarifying pure liquid sulfur after filtering by filter, content 99.8% enters heating reaction furnace through the pressurization of sulphur metering pump （2）；
（b）The gaseous mixture that the molar content for taking coal bed gas is more than 96%, according to the gaseous mixture after coal bed gas compensator pressure regulation In carbon and sulphur molar ratio be 1: 2-3 raw material proportioning carry out dispensing, theoretically sulfur consumption general excessive 5%, need to prevent Only methane thermal cracking generates carbon black, is 800- in gauge after dispensing is preheated to 300-500 DEG C in reacting furnace Under the conditions of 1000kPa, high temperature non-catalytic reaction is carried out under the conditions of 650-700 DEG C, then whole process streams enter adiabatic reaction In device, reaction time reacted generation carbon disulfide with the sulfur vapor overheated for 5-10 seconds.Due to the addition and change of coal bed gas Learn reaction progress, decompression, high-sulfur molecular dissociation, gaseous mixture come out of the stove after enter reacting furnace after enter reactor the reaction was continued.Make Outlet reaches 98.8% conversion ratio, with methanometer；
（c）The complete sulphur condensation of unreacted（3）For liquid, into catching sulphur device（4）, the liquid sulfur after trapping is by by sulphur device（5） Boiling is carried out, is entered by the gaseous state carbon disulfide that the boiling of sulphur device comes out and catches sulphur device, liquid sulfur enters flash vessel（6）, liquid sulfur exists Further boiling is carried out in molten sulfur flash vessel, gas enters water seal recycling carbon disulfide, and liquid sulfur is put into sulfur melting groove；
（d）It catches the decompression of sulphur device Process Gas regulating valve and enters carbon disulfide water condenser（7）, gas passes through carbon disulfide water condenser Carbon disulfide is condensed into liquid, carbon disulfide water condenser gas enters carbon disulfide brine condenser（8）, carry out further Sub-cooled, by H in liquid carbon disulphide2S is detached；
（e）Liquid carbon disulphide enters refining desulfurization tower（9）, gas enters H2S water coolings and vulcanization hydrogen salt are cold, pass through sub-cooled Afterwards（10）, liquid carbon disulphide enters destilling tower（11）, destilling tower steams the incoagulable gas in carbon disulfide, carbon disulfide Liquid is by H2Enter reservoir area storage tank after S water coolings and the cold sub-cooled of salt；
（f）The cold middle H of carbon disulfide salt2S gases enter Crouse's hydrogen sulfide surge tank, enter back into Crouse's combustion furnace（12）It carries out Combustion reaction Recovered sulphur, vulcanization hydrogen salt cold air enter water seal recycling carbon disulfide, and gas enters Crouse's incinerator through burning Can toxic tail gas be converted with almost all after burning, then take double calcium method desulfurization technologies（13）Generate calcium sulfate（Gypsum）, so as to real Show the recycling of sulphur and recycle.
In order to prepare clean molten sulfur, which is also provided with molten sulphur, filtration system, in order to cool down saline solution, is additionally provided with Compressor and freeze system.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art The content of the present invention can be understood and implemented according to this, it is not intended to limit the scope of the present invention, every according to this hair Equivalent change or modification made by bright Spirit Essence, is all included within the scope of the present invention.

Claims (6)

  1. It is 1. a kind of using coal bed gas as the method for Material synthesis carbon disulfide, which is characterized in that include the following steps：
    （1）Solid sulfur is molten sulfur with steam indirectly heat by sulfur melting groove, and molten sulfur is pumped into filter by liquid sulfur pump, is passed through It obtains clarifying pure liquid sulfur after filter filtering, content 99.8% enters heating reaction furnace through the pressurization of sulphur metering pump；
    （2）Molten sulfur is reacted with coal bed gas in heating reaction furnace to be generated carbon disulfide and hydrogen sulfide process gas and passes through reactor Further reaction；
    （3）The complete sulphur condensation of unreacted is liquid, and into sulphur device is caught, the liquid sulfur after trapping is passed through is carried out boiling by sulphur device, Entered by the gaseous state carbon disulfide that the boiling of sulphur device comes out and catch sulphur device, liquid sulfur enters flash vessel, and liquid sulfur is in molten sulfur flash vessel Further boiling is carried out, gas enters water seal recycling carbon disulfide, and liquid sulfur is put into sulfur melting groove；
    （4）It catches sulphur device Process Gas and enters carbon disulfide water condenser, gas is cold by carbon disulfide by carbon disulfide water condenser It coagulates for liquid, carbon disulfide water condenser gas enters carbon disulfide brine condenser, carries out further sub-cooled, by liquid Hydrogen sulfide detaches in carbon disulfide；
    （5）Liquid carbon disulphide enters refining desulfurization tower, and gas enters hydrogen sulfide water cooling and vulcanization hydrogen salt is cold, passes through sub-cooled Afterwards, liquid carbon disulphide enters destilling tower, and destilling tower steams the incoagulable gas in carbon disulfide, and carbon disulfide liquid is by sulphur Enter reservoir area storage tank after changing hydrogen water cooling and the cold sub-cooled of salt；
    （6）The cold middle hydrogen sulfide gas of carbon disulfide salt enters Crouse's hydrogen sulfide surge tank, enters back into the progress of Crouse's combustion furnace Combustion reaction Recovered sulphur, vulcanization hydrogen salt cold air enter water seal recycling carbon disulfide, and gas enters Crouse's incinerator through burning Burn, convert toxic tail gas, then take double calcium method desulfurization technologies generation calcium sulfate, so as to fulfill sulphur recycling and recycle.
  2. It is 2. according to claim 1 using coal bed gas as the method for Material synthesis carbon disulfide, it is characterised in that：Choose coal seam The molar content of gas methane is more than 96% gaseous mixture, is 1: 2-3 according to the carbon in the gaseous mixture and the molar ratio of sulphur Raw material proportioning carries out dispensing.
  3. It is 3. according to claim 2 using coal bed gas as the method for Material synthesis carbon disulfide, it is characterised in that：By methane with Sulphur steam mixes, and methane gas phase is made to carry out vulcanization reaction in two series connection are without the fixed bed reactors of catalyst.
  4. 4. 650-700 DEG C is heated to when no silica gel, aluminium oxide or bauxite are when catalyst to get to the mixing containing carbon disulfide Gas after recycling unreacted sulphur, methane and impurity hydrogen sulfide, condenses to obtain carbon disulfide product.
  5. It is 5. according to claim 5 using coal bed gas as the method for Material synthesis carbon disulfide, it is characterised in that：To technique tail CS in gas2Reservoir area storage tank is entered using the cure method of hydrogen water cooling and the cold sub-cooled of salt of carbon disulfide liquid, improves production Product yield, so as to accordingly decrease product energy consumption.
  6. It is 6. according to claim 6 using coal bed gas as the method for Material synthesis carbon disulfide, it is characterised in that：By attached production H2S is converted into sulphur, and for unconverted hydrogen sulfide and remains in other sulfide in tail gas in claus oven high temperature Calcining can be converted into the smaller SO of toxicity with almost all2, then take double calcium method desulfurization technology generation calcium sulfate（Gypsum）, so as to It realizes the recycling of sulphur and recycles, economic benefit is made to reach maximization.
CN201710242801.2A 2017-04-14 2017-04-14 It is a kind of using coal bed gas as the method for Material synthesis carbon disulfide Withdrawn CN108128776A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710242801.2A CN108128776A (en) 2017-04-14 2017-04-14 It is a kind of using coal bed gas as the method for Material synthesis carbon disulfide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710242801.2A CN108128776A (en) 2017-04-14 2017-04-14 It is a kind of using coal bed gas as the method for Material synthesis carbon disulfide

Publications (1)

Publication Number Publication Date
CN108128776A true CN108128776A (en) 2018-06-08

Family

ID=62388401

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710242801.2A Withdrawn CN108128776A (en) 2017-04-14 2017-04-14 It is a kind of using coal bed gas as the method for Material synthesis carbon disulfide

Country Status (1)

Country Link
CN (1) CN108128776A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1389397A (en) * 2002-07-02 2003-01-08 辽阳瑞兴化工有限公司 Production process of CS2 and H2S with mixed natural gas of methane and ethane
CN1422804A (en) * 2002-12-31 2003-06-11 王起超 Method for collecting and treating excess sulphur and elemental carbon from process gas of carbon bisulfide production
US20080260615A1 (en) * 2005-03-31 2008-10-23 Council Of Scientific & Industrial Research Process for the preparation of micron/nano sized inorganic material
CN102153053A (en) * 2010-11-20 2011-08-17 辽宁瑞兴化工集团有限公司 Methods for purifying and comprehensively utilizing hydrogen sulfide byproduct during production of carbon disulfide by methane method
CN103480252A (en) * 2012-06-13 2014-01-01 中国石油天然气股份有限公司 Method for treating acid gas containing hydrogen sulfide

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1389397A (en) * 2002-07-02 2003-01-08 辽阳瑞兴化工有限公司 Production process of CS2 and H2S with mixed natural gas of methane and ethane
CN1422804A (en) * 2002-12-31 2003-06-11 王起超 Method for collecting and treating excess sulphur and elemental carbon from process gas of carbon bisulfide production
US20080260615A1 (en) * 2005-03-31 2008-10-23 Council Of Scientific & Industrial Research Process for the preparation of micron/nano sized inorganic material
CN102153053A (en) * 2010-11-20 2011-08-17 辽宁瑞兴化工集团有限公司 Methods for purifying and comprehensively utilizing hydrogen sulfide byproduct during production of carbon disulfide by methane method
CN103480252A (en) * 2012-06-13 2014-01-01 中国石油天然气股份有限公司 Method for treating acid gas containing hydrogen sulfide

Similar Documents

Publication Publication Date Title
US20180065851A1 (en) Setr- super enhanced tail gas recovery; a tail gas process with adsorbent reactors for zero emissions
CN106467293B (en) A kind of method for producing sulphur and the system and device for producing sulphur
CN103079993A (en) Methods and apparatus for sulfur recovery from acid gases
CN110180383B (en) Hydrogen sulfide acid gas and hydrogen sulfide resource cooperative recovery device and method
US20220306952A1 (en) Process for treating a feedstock comprising halides
CN102951613A (en) Catalyst grading method and technique of acid gas treatment sulfur recycling device
CN204874343U (en) Marsh gas and coke oven gas joint production methyl alcohol device
CA1172428A (en) Process for reacting hydrogen sulphide with oxygen
US3758676A (en) Method for recovery of elemental sulfur from sour gas
CN101239705A (en) Method for obtaining high-purity sulfur from gas containing hydrogen sulfide
CN101565172B (en) Method for recovering sulfur from byproduct of acid gas generated in production of rubber chemicals
CN108128776A (en) It is a kind of using coal bed gas as the method for Material synthesis carbon disulfide
CN202864918U (en) Waste gas treatment system of acid gas
CN101792129B (en) Application of II-stage reactor in sulfur recovery industry
CN110143571A (en) The apparatus and method of the hydrogen manufacturing of environment-friendly type hydrogen sulfide and insoluble sulfur
CN107789969A (en) The processing method and device of a kind of sour gas
CN105642090B (en) A kind of Acidic Gas Treating method and device
CN114261964A (en) Method and device for treating carbon dioxide feed gas
CN103484182A (en) Method for producing substitute natural gas through CO-rich industrial tail gas
EP0059548A1 (en) Method and apparatus for treating sulfur-containing gas stream
US2220357A (en) Synthetical production of liquid hydrocarbons from carbon monoxide and hydrogen
CN112940797A (en) Coke oven gas fine desulfurization system
CN208249887U (en) A kind of hydrogen generating system
CN103906558A (en) Staged combustion of combustible sulphur-containing effluents with recovery of the sulphur in the CLAUS process
CN110272026A (en) The device and method of hydrogen sulfide sour gas thermocatalytic recycling hydrogen and insoluble sulfur

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication

Application publication date: 20180608

WW01 Invention patent application withdrawn after publication