CN1182028C - Method for collecting and treating excess sulphur and elemental carbon from process gas of carbon bisulfide production - Google Patents
Method for collecting and treating excess sulphur and elemental carbon from process gas of carbon bisulfide production Download PDFInfo
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- CN1182028C CN1182028C CNB021281491A CN02128149A CN1182028C CN 1182028 C CN1182028 C CN 1182028C CN B021281491 A CNB021281491 A CN B021281491A CN 02128149 A CN02128149 A CN 02128149A CN 1182028 C CN1182028 C CN 1182028C
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Abstract
The present invention relates to a method for collecting and treating excess sulphur and simple substance carbon from process gas of carbon bisulfide production, which is characterized in that process gas which is off from a carbon disulfide reactor is at least washed and collected once with liquid sulfur as a scrubbing medium, and then, the process gas is at least washed and collected once with liquid state carbon disulfide as the scrubbing medium, wherein the process gas is washed and collected in a mode of entering and passing through the liquid sulfur and the liquid state carbon disulfide scrubbing medium, and then, the process gas enters a condensation separation treating process of carbon disulfide. The method effectively solves the problems of clogging pipes by mud objects formed by the difficultly removed powdery simple substance carbon generated because of cracking of surplus sulfur and hydrocarbon in the process gas and sulfur corrosion to equipment pipes by high temperature process gas in the present carbon disulfide production.
Description
Technical field
What the present invention relates to is being in the process of raw material production dithiocarbonic anhydride with hydro carbons and sulphur, to the superfluous sulphur in the process gas that leaves the dithiocarbonic anhydride reactor, and the treatment process that captures removal because of the simple substance carbon that cracking produced of hydrocarbon raw material.
Background technology
When being raw material production dithiocarbonic anhydride with rudimentary hydro carbons such as sulphur and methane or the oil gas that contains saturated and/or unsaturated lower carbon number hydrocarbons, except that all adopt usually make sulphur excessive, also can produce the simple substance carbon of powdered granule form in the reaction process because of the cracking of hydrocarbon raw material.Therefore, in the process gas of the form of mixtures of leaving the dithiocarbonic anhydride reactor and forming, be attended by superfluous sulphur and be inevitable and unavoidable by the powdery simple substance carbon that hydrocarbon cracking produces by resultant of reaction and unreacted reactant.Before sending into later condenser system,, will stop up process pipeline and equipment if earlier these superfluous sulphur and powdery simple substance carbon in the process gas are not removed.
It is reported, at present when company such as U.S. FMC and domestic enterprise adopt these class methods to produce dithiocarbonic anhydride, to leaving the process gas behind the reactor, all just adopt the mode of condensation, make process gas be cooled to 140 ℃-160 ℃ by about 650 ℃, so that wherein unreacted superfluous sulphur is condensed into liquid state by gaseous state and separates, and do not do special the processing by the powdery simple substance carbon that hydrocarbon cracking produced to simultaneously existing, just after carrying out heat exchange, horizontal heat exchanger sends into the condensation separation process of later dithiocarbonic anhydride and hydrogen sulfide.Owing to be difficult to fully fully with the removal of the mode of condensation liquefaction to the superfluous sulphur in the process gas, therefore in the continuous process of cooling of postorder, particularly be generally when carrying out the dithiocarbonic anhydride condensation separation under-20 ℃～30 ℃ conditions in temperature, the condensation that is liquefied that also can keep of these remaining sulphur, and mix and form with the powdery simple substance carbon that deposits and lack mobile " sulphur mud " aggregation.Find in the production practice, the major reason that these " sulphur mud " still do not cause heat exchanger tube heat exchange effect to descend, and also regular meeting causes the obstruction of the tubulation and the process pipe of interchanger, causes having to stopping production and cleans, and influenced carrying out continuously of producing.Simultaneously, when 640 ℃～680 ℃ pyroprocess gas were carried out heat exchange, the serious high-temperature sulfidation attack of heat exchanging equipment also was influence and the important factor that significantly shortens service life of equipment.
Summary of the invention
The present invention will provide a kind of and produce with sulphur and hydrocarbon raw material in the process of dithiocarbonic anhydride, to existing superfluous sulphur in the process gas that leaves the dithiocarbonic anhydride reactor and the treatment process that captured removal by the powdery simple substance carbon that cracking produced of hydrocarbon raw material.The inventive method can make the superfluous sulphur and the powdery simple substance carbon that are present in the process gas can reach the basic degree of all removing, thereby solve the blockage problem of process pipes such as " sulphur mud " form aggregation heat exchanging device tubulation satisfactorily.
Another object of the present invention, be superfluous sulphur in making process gas and powdery simple substance carbon can realize satisfactorily by basic all capture remove in, can also make pyroprocess gas enter follow-up heat exchange, equipment such as condensation, temperature during pipeline can be greatly reduced, from having solved pyroprocess gas heat exchanging equipment equally satisfactorily, the serious high-temperature sulfidation attack problem at heat exchanging equipment import position particularly, can prolong the work-ing life of equipment greatly, and can make the common at present equipment such as tubulation of employing high-class stainless steel that need to change the use plain carbon stool into, can further reduce cost, improve overall economic efficiency.
The capture treatment process of superfluous sulphur and simple substance carbon in the carbon disulphide production process gas of the present invention, be to make the process gas that leaves the dithiocarbonic anhydride reactor wash capture at least once with liquid sulfur as washing medium earlier, reusable liquid dithiocarbonic anhydride washs capture once at least as washing medium, and then sends into the condensation separation treating processes of dithiocarbonic anhydride.
In above-mentioned treatment process, said the best washing capture mode to process gas is all to adopt to make the process gas that is washed to enter and to be undertaken by the mode of liquid washing medium.
So that be washed the method that gas washs by the mode of liquid washing medium, existing at present report and/or the method that has been used are a lot.These methods can be used in above-mentioned treatment process of the present invention undoubtedly.Through test, can be used as special recommendation and can supply one of method that adopts, be that to adopt the present technique contriver application number that patented already be that 02276560.3 technology is carried out, that is: make to be washed gas and to be undertaken by the mode of liquid washing medium by the lower end of in the washing plant container, stretching into the subsurface iris type structure of liquid washing medium; Can be for the another kind of method that adopts and recommend, be in the equipment of similar form, make to be washed gas, undertaken by the mode of liquid washing medium in the bubbling mode by in the washing plant container, stretching into the subsurface lower edge of liquid washing medium with bubble-cap formula structure of toothed edge.The basic structure of said this form washing plant and principle, be to hold in the container type structure of storing liquid washing medium in the bottom, be provided with one lower edge be submerged in barrier structure under the washing medium liquid level---maybe can realize the structure of other appropriate form of same working process as iris type structure, bubble-cap formula structure, and above this tankage, also form two separate space of mutual separation by this barrier structure.During washing, be washed gas and can only enter washing medium by what a side space was sent into, and cross the lower edge that is submerged in subsurface this barrier structure of washing medium, just can enter another space.Be washed gas and in washing medium, enter this process of those spatial, can be washed medium and wash by (being generally the mode of bubbling or similar bubbling) in space thus.Above-mentionedly be present in the superfluous sulphur of unreacted in the process gas the time, can be melted into and/or be dissolved in wherein by liquid sulfur and/or liquid carbon disulphide washing medium; Existing powdery simple substance carbon also can be left in the liquid washing medium simultaneously.Test shows that the mode that only adopts liquid sulfur to wash merely captures and remove the efficient of superfluous sulphur in the process gas, just can be higher than the removal of the present conventional condensing mode that adopts to superfluous sulphur far away.
Therefore the fusing point of sulphur is 119 ℃, and the temperature of said liquid sulfur as washing medium generally may be controlled to 120 ℃-170 ℃ and gets final product in aforesaid method, particularly to be controlled at 120 ℃-150 ℃ scope for well.
The dithiocarbonic anhydride that is used to wash, then generally convenient to use by the not refining dithiocarbonic anhydride crude product that obtains in the preorder production process.
Generally speaking, when adopting aforesaid method of the present invention, one of reference method when can be used as concrete enforcement, be adopt said process gas captured 2-3 time with the liquid sulfur washing after, reusable liquid dithiocarbonic anhydride washing mode is once handled, and can obtain satisfied washing effect.Wherein, adopt above-mentioned making to be washed gas when process gas is captured with liquid sulfur washing first and undertaken by the mode of liquid washing medium by the lower end of stretching into the subsurface iris type structure of liquid sulfur medium in the washing plant container, later each time washing capture then can be adopted above-mentioned making to be washed gas to be undertaken by the mode of washing medium by stretching into the subsurface lower edge with bubble-cap formula structure of toothed edge of liquid washing medium in the washing plant container.Through test, after the secondary liquid sulfur scrubber captures, can reach more than 95% the capture clearance of superfluous sulphur in the process gas, more can reach more than 99% the capture clearance of simple substance carbon.
Capture in the treating processes in above-mentioned washing, because process gas just directly adopts aforesaid method of the present invention to handle after leaving reactor, therefore, after twice above-mentioned liquid sulfur washing capture, when superfluous sulphur of the existing overwhelming majority and powdery simple substance carbon capture and remove in process gas, can also make the process gas when leaving reactor be reduced to 400 ℃-430 ℃, thereby reduce the disadvantageous effect of high-temperature sulfidation attack effectively the equipment pipes such as heat exchange of postorder by 640 ℃-680 ℃ high temperature.
For the energy in the production process is fully utilized to greatest extent, save energy, in above-mentioned treatment process, can wash once back of capture at least with the liquid sulfur washing medium---generally can after capture 1～2 time, the liquid sulfur washing after vertical pipe type interchanger carries out heat exchanging process, continue subsequent washing again and capture.To washing process gas after most superfluous sulphur and simple substance carbon have once been removed in capture at least with liquid sulfur, adopt the vertical pipe type interchanger of vertical installation form to carry out heat exchange again, rather than employing horizontal heat exchanger mode commonly used at present, biggest advantage and purpose are, even if a small amount of " the sulphur mud " that also may produce at heat transfer process, the bottom that also can drop to equipment naturally because of himself action of gravity in vertical equipment is easy to be eliminated, thereby further prevents and avoided the blocked possibility of heat exchanger tube effectively.If necessary, the process gas after heat exchange can also capture once by the reusable liquid sulfur scrubber, further removes remaining a small amount of superfluous sulphur and simple substance carbon, and then washs capture with liquid carbon disulphide.
Dithiocarbonic anhydride is the splendid solvent of a kind of solubility property, therefore after washing capture with dithiocarbonic anhydride as washing medium more at last, last remaining sulphur (and the simple substance carbon that can not exist the again general this moment) removal that promptly can be captured substantially is clean in the process gas.Make the process gas after this thorough purifying treatment, can continue to be admitted to the isolating condensation process process of follow-up dithiocarbonic anhydride and hydrogen sulfide.At this moment,, the phenomenon of " sulphur mud " blocking pipe also can not occur, advantageously guarantee and improved the quality of resulting dithiocarbonic anhydride product even if under-20 ℃～30 ℃ dithiocarbonic anhydride condensing temperature.Simultaneously,, can also make temperature further drop to 50 ℃-56 ℃ from 140 ℃-170 ℃, thereby can alleviate the load of follow-up dithiocarbonic anhydride condenser greatly, help improving the yield of dithiocarbonic anhydride product at last with the process gas after the dithiocarbonic anhydride washing.
If desired, above-mentioned said process gas is carried out heat exchange with vertical pipe type interchanger before, can also increase once the process of carrying out heat exchange with tube exchanger earlier again.
With the liquid sulfur is the superfluous sulphur that the medium washing captures back, is re-used as raw material after can reclaiming again and uses.As the dithiocarbonic anhydride of washing medium, equally also can be by operations such as rectification and purification, will wherein capture impurity separation such as dissolved sulphur and purifying treatment after, the conduct raw material sulphur that can be reused respectively, and become required dithiocarbonic anhydride product.These processing and operation can be adopted existing at present report or pass through to realize at the corresponding mature technology that widely uses.
Be understood that in sum, be in the process of raw material production dithiocarbonic anhydride with hydro carbons and sulphur, treatment process of the present invention is not only simple and easy to do, and can make the superfluous sulphur in the process gas that leaves the dithiocarbonic anhydride reactor and effectively and satisfactorily be captured Ex-all because of simple substance carbon that hydrocarbon cracking produced, both prevented and avoided making the production unit pipeline to be stopped up by " sulphur mud ", reduced the running cost of production.Simultaneously, method of the present invention can also reduce high temperature vulcanized to equipment, Corrosion of Pipeline significantly, greatly helps prolonging the work-ing life of equipment.And, the equipment such as tubulation that need the employing high-class stainless steel at present usually can be changed into adopt common carbon steel, further greatly reduce cost, overall economic efficiency is remarkable.
According to foregoing,,, can also make modification, replacement or the change of various ways not breaking away under the above-mentioned basic fundamental thought of the present invention prerequisite according to the ordinary skill knowledge and the customary means of this area.
Below in conjunction with embodiment, foregoing of the present invention is described in further detail again by the accompanying drawing illustrated embodiment.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.All technology that realizes based on foregoing of the present invention all belong to scope of the present invention.
Description of drawings
Fig. 1 is a kind of schematic flow sheet that capture treatment process of the present invention to superfluous sulphur and simple substance carbon in the carbon disulphide production process gas.
Embodiment
As shown in the figure be a kind of flow process that capture treatment process of the present invention to superfluous sulphur and simple substance carbon in the carbon disulphide production process gas.Its process is as follows:
With amount of natural gas is 282 mark cubic meters/hour (consist of methane 96.37%, ethane 1.62%, propane 0.45%, 0 butane 33%), with the sulphur that surpasses theoretical amount 6% be raw material, after under 640 ℃～680 ℃ and 0.4Mpa condition, finishing the reaction of synthetic dithiocarbonic anhydride, the form of mixtures process gas that leaves the dithiocarbonic anhydride reactor is 120 ℃-170 ℃ through excess temperature earlier, particularly 120 ℃ of-150 ℃ of liquid sulfur washings capture once, adopting above-mentioned number of patent application during washing is 02276560.3 industrial gasses washing plant, and process gas is undertaken by the mode of liquid washing medium by the lower end of stretching into the subsurface iris type structure of liquid washing medium in the washing plant container.Then the process pneumatic transmission is gone into second stage molten sulfur washing plant, the molten sulfur washing medium that captures as washing temperature-resistant, adopt similar equipment during washing, make to be washed gas, undertaken by the mode of liquid washing medium in the bubbling mode by stretching into the subsurface lower edge of liquid washing medium in the washing plant container with bubble-cap formula structure of toothed edge.Process temperature degree after secondary molten sulfur washing captures is reduced to 400 ℃～430 ℃ by can be when going out reactor 640 ℃～680 ℃, is present in the process gas 95% or more superfluous sulphur and 99% above powdery simple substance carbon and has been washed capture and puts and stay in the molten sulfur washing medium.Afterwards process gas successively carries out (heat energy that exchanges out is used for the heating of production process) after the heat exchange through a vertical disc cast interchanger and a vertical pipe type interchanger successively, the temperature of process gas can further drop to the boiling point (＜444.6 ℃) that is lower than sulphur, thereby has avoided high temperature vulcanized corrosion to equipment effectively.And then make this process gas successively more respectively by being above-mentioned same bubble-cap formula washing plant, carry out a molten sulfur (the molten sulfur temperature is a same) washing capture and a liquid carbon disulphide washing capture.Superfluous sulphur and simple substance carbon remaining in the process gas after the washing can be captured Ex-all substantially, and make the temperature of process gas drop to 50 ℃～56 ℃ at last.Scavenging process gas after the processing can be sent to postorder and the isolating dithiocarbonic anhydride condensation process of hydrogen sulfide process.Washing captures used liquid carbon disulphide medium, for by resulting still unpurified dithiocarbonic anhydride crude product in the preorder production process.
Collected sulphur can be sent in the lump and catch the recovery of sulphur device in processes such as above-mentioned washing capture and heat exchange, after respective handling such as flash distillation and purification, is reused as raw material sulphur.Washing captures used coarse carbon bisulfide by rectifying, after wherein impurity such as residual sulphur separate, promptly becomes purified dithiocarbonic anhydride product.
Claims (10)
1. the capture treatment process of superfluous sulphur and simple substance carbon in the carbon disulphide production process gas, it is characterized in that making the process gas that leaves the dithiocarbonic anhydride reactor is that washing medium washs capture once at least with the liquid sulfur earlier, reusable liquid dithiocarbonic anhydride is that washing medium washs capture once at least, and then sends into the condensation separation treating processes of dithiocarbonic anhydride.
2. capture treatment process as claimed in claim 1, employing makes processed process gas to enter and to be undertaken by the mode of liquid washing medium to it is characterized in that capturing said washing to process gas all.
3. capture treatment process as claimed in claim 1 or 2, the temperature that it is characterized in that said liquid sulfur washing medium are 120 ℃-170 ℃.
4. capture treatment process as claimed in claim 1 or 2, the liquid carbon disulphide washing medium that it is characterized in that being used for washing capture is the resulting refining dithiocarbonic anhydride crude product of preorder production process.
5. capture treatment process as claimed in claim 1 or 2 is characterized in that the washing of process gas captured to adopt to make being washed gas and being undertaken by the mode of liquid washing medium by the lower end of stretching into the subsurface iris type structure of liquid washing medium in the washing plant container.
6. capture treatment process as claimed in claim 1 or 2 is characterized in that it is to make to be washed gas and to be undertaken by the mode of liquid washing medium by stretch into the subsurface lower edge with bubble-cap formula structure of toothed edge of liquid washing medium in the washing plant container that the washing of process gas is captured what adopt.
7. capture treatment process as claimed in claim 1 or 2, adopt when it is characterized in that making process gas to capture with liquid sulfur washing first to make to be washed gas and to be undertaken by the mode of liquid washing medium by the lower end of stretching into the subsurface iris type structure of liquid sulfur medium in the washing plant container, later each time washing captures then all employings and makes and be washed gas and undertaken by the mode of washing medium by stretch into the subsurface lower edge with bubble-cap formula structure of toothed edge of liquid washing medium in the washing plant container.
8. capture treatment process as claimed in claim 1 or 2, it is characterized in that said process gas captures 2-3 time with liquid sulfur washing after, reusable liquid dithiocarbonic anhydride washing capture is once.
9. capture treatment process as claimed in claim 8 is characterized in that after said process gas washs capture once at least with liquid sulfur, continues subsequent washing again and capture after vertical pipe type interchanger carries out heat exchange.
10. capture treatment process as claimed in claim 9 is characterized in that said process gas earlier carries out heat exchange through a tube exchanger before carrying out heat exchange entering vertical pipe type interchanger.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021281491A CN1182028C (en) | 2002-12-31 | 2002-12-31 | Method for collecting and treating excess sulphur and elemental carbon from process gas of carbon bisulfide production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021281491A CN1182028C (en) | 2002-12-31 | 2002-12-31 | Method for collecting and treating excess sulphur and elemental carbon from process gas of carbon bisulfide production |
Publications (2)
| Publication Number | Publication Date |
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| CN1422804A CN1422804A (en) | 2003-06-11 |
| CN1182028C true CN1182028C (en) | 2004-12-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB021281491A Expired - Lifetime CN1182028C (en) | 2002-12-31 | 2002-12-31 | Method for collecting and treating excess sulphur and elemental carbon from process gas of carbon bisulfide production |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105080172A (en) * | 2015-06-25 | 2015-11-25 | 辽宁瑞兴化工集团有限公司 | Desulfurating rectifying tower for manufacturing carbon disulfide by virtue of high pressure non-catalytic natural gas method |
| CN108128776A (en) * | 2017-04-14 | 2018-06-08 | 阳城县瑞兴化工有限公司 | It is a kind of using coal bed gas as the method for Material synthesis carbon disulfide |
| CN108483446B (en) * | 2018-04-10 | 2021-12-10 | 上海东庚化工技术有限公司 | Method and system for separating excessive sulfur in carbon disulfide production process |
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2002
- 2002-12-31 CN CNB021281491A patent/CN1182028C/en not_active Expired - Lifetime
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Effective date of registration: 20210823 Address after: 610300 No. 22, building 2, No. 7, Hongyang safety lane, Qingbaijiang District, Chengdu, Sichuan Patentee after: Wang Qichao Address before: Qingbaijiang District of Chengdu City, Sichuan Province, 610300 lane security Kegon town building 22, No. 7, 2 Patentee before: Wang Qichao Patentee before: Wang Gang |
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Effective date of registration: 20211019 Address after: 636150 Puguang micro glass fiber new material industrial park, Xuanhan County, Dazhou City, Sichuan Province Patentee after: Xuanhan Zhengbei Technology Co.,Ltd. Address before: 610300 No. 22, building 2, No. 7, Hongyang safety lane, Qingbaijiang District, Chengdu, Sichuan Patentee before: Wang Qichao |
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Granted publication date: 20041229 |