CN103436285A - Sulphur supplement process for coal tar hydrogenation device - Google Patents
Sulphur supplement process for coal tar hydrogenation device Download PDFInfo
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- CN103436285A CN103436285A CN2013103743406A CN201310374340A CN103436285A CN 103436285 A CN103436285 A CN 103436285A CN 2013103743406 A CN2013103743406 A CN 2013103743406A CN 201310374340 A CN201310374340 A CN 201310374340A CN 103436285 A CN103436285 A CN 103436285A
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- coal tar
- hydrogen sulfide
- sulphur
- hydrogen
- hydrogenation device
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Abstract
The invention discloses a sulphur supplement process for a coal tar hydrogenation device. The sulphur supplement process comprises the step of compressing hydrogen sulphide in a return tank on the top of a single stripping tower to the inlet of a reactor by a reciprocating compressor, so as to ensure the concentration of the hydrogen sulphide of a high-voltage system. By coordinating work-starting step sequences, the work-starting and work-stopping time of the single stripping tower and the coal tar hydrogenation device is buffered by a sulphur-containing sewage storage tank, thus guaranteeing that the process can still be utilized during work-starting (not for the first time) and pre-sulfuration for the coal tar hydrogenation device.
Description
Affiliated technical field
The present invention relates to the benefit sulphur of coal tar hydrogenating unit, specifically, is follow-on by coal tar hydrogenating unit reactive system proper site injecting gas hydrogen sulfide, to keep in the reactive system recycle hydrogen hydrogen sulfide content in reasonable level.
Background technology
The technique of at present coal tar being produced to vehicle fuel by high-pressure hydrogenation is more and more ripe.The technology such as the hydrogenation technique by improving oil refining industry and catalyzer, can very effectively remove the foreign material such as sulphur in coal tar, nitrogen, polycyclic aromatic hydrocarbons, again by hydrocracking will than diesel oil more the heavy constituent cracking be diesel oil and light constituent more, realize reluctant coal tar is converted into to clear gusoline.
Following table provides the properties of coalite tar in certain:
| Density (kg/m 3) | 1030 |
| Carbon residue (w%) | 4.0 |
| Phenol (w%) | 15.3 |
| Total nitrogen (w%) | 0.79 |
| Sulphur (w%) | 0.33 |
| Stable hydrocarbon (w%) | 21 |
| Aromatic hydrocarbon (w%) | 54 |
| Colloid+bituminous matter (w%) | 25 |
| Cetane index | ＜20 |
Oiliness analysis according to coal tar, visible its nitrogen content is higher than sulphur content, so the ammonia produced after hydrogenation will, more than hydrogen sulfide, adopt the front water filling of air cooler, utilize ammonia solubleness in water very large, form ammonia soln and absorb cleanly the hydrogen sulfide in reaction effluent.Maintain the sulphided state catalyzer (Ni of coal tar hydrogenating
3s
2, MoS
2deng) high reactivity, often to reactive system or fresh feed pump entrance, inject vulcanizing agent DMDS in operation, to keep hydrogen sulfide content in the recycle hydrogen system, in the 500-1000ppm left and right, to avoid hydrogen sulfide content, descend.Lack the protection of hydrogen sulfide, hydrogen easily is reduced into the simple substance state by noble metal sulphided state on catalyzer, catalyst hydrogenation activity is seriously reduced, even permanent deactivation.On the other hand, in tar, aromatic hydrocarbon and gum asphalt total content reach 79%, necessarily require higher hydrogen dividing potential drop (18Mpa usually) and catalyst activity could realize its deep refining and cracking.Therefore, for coal tar hydrogenating, reaction seems abnormal urgent to extra benefit sulphur.
The benefit sulphur method of traditional technology is, to the reaction feed pump intake or to the reactive system furnace outlet, injects vulcanizing agent DMDS (Methyl disulfide), after DMDS injects reactive system, under reaction conditions, with hydrogen reaction, produces hydrogen sulfide, and reaction formula is as follows:
CH
3-S-S-CH
3+3H
2＝2CH
4+2H
2S
For ammonia and the hydrogen sulfide that prevents from producing after hydrogenation crystallizes into salt obstruction air cooler in process of cooling, before the high-pressure air cooler of being everlasting, water filling is to dissolve this salt.For processing the sour water of hydrogenation unit, set up and put Sulfur-containing Sewage Stripping Tower to isolate ammonia and hydrogen sulfide.Sour water stripping, adopt single tower flow process usually, and, under the bottom reboiler heating condition, tower top goes out hydrogen sulfide, goes out ammonia+water vapour gas mixture in tower, at the bottom of tower for purifying waste water.Single tower stripping tower adopts the total reflux form, with purification tower top gas hydrogen sulfide.
Because high-pressure system maintains catalyst activity, keep hydrogen sulfide to be in excess in ammonia, make in reaction effluent to contain a small amount of hydrogen sulfide, final product needed desulfurization.General method is to reacting low minute desulfurization, fuel gas desulfurization and desulfuration of liquefied gas, desulfurization adopts MDEA (n-formyl sarcolysine base diethanolamine) solution, the MDEA solution that has absorbed hydrogen sulfide collects into regenerator column top, under the bottom reboiler heating condition, tower top goes out hydrogen sulfide, and the MDEA solution circulated be purified at the bottom of tower is used.The MDEA solution regenerator adopts the total reflux form, with purification tower top gas hydrogen sulfide.
Patent CN93121026.7 has introduced a kind of benefit sulphur scheme of hydrotreatment, introduced to the arbitrary position of reactive system and its recommended location and injected sour product, existing problems are that this oil product has dissolved hydrogen sulfide at medium low pressure system, in high-pressure system, equally hydrogen sulfide can be taken away; If can bring crude oil to problems such as Coal Chemical Engineering Project conveyings but select high-sulpur crude etc. to make sulfur supplementary agent, economically not as direct purchase DMDS; This patent has also been introduced and can have been injected hydrogen sulfide containing gas, but the injection phase of recommending is the fresh feed pump entrance, but, by gas inject impeller pump entrance, can cause pump cavitation and find time.
Summary of the invention
For supplementing the sulphur disappearance of coal tar hydrogenating unit high-pressure system, maintain sulphur budget, keep catalyst activity, this technique is by arranging the hydrogen sulfide compressor, hydrogen sulfide by single tower stripping return tank of top of the tower and/or amine liquid regeneration overhead return tank, be compressed to the hydrogenator entrance.Be injected into the hydrogen sulfide flow of reactor inlet by regulating this compressor, in control reactive system recycle hydrogen, hydrogen sulfide content is at 500-1000ppm.Because this hydrogen sulfide compressor has the advantages that pressure ratio is high, flow is little, should adopt reciprocating engine, the Flow-rate adjustment mode of specifically taking, can according to the device operating mode choose pass step by step return, the modes such as sniff valve time-delay closing, frequency conversion.
For solving the go into operation source of the required hydrogen sulfide of stage catalyst prevulcanized of coal tar hydrogenating unit, this technique goes into operation and walks order and realize by coordinating single tower stripper plant and coal tar hydrogenating unit.Specifically, intermediate buffering tank field by sour water, before coal tar hydrogenating unit is stopped work, single tower stripper plant first stops work to store sour water, before hydrogenation unit goes into operation catalyst vulcanization, single tower stripper plant first goes into operation and processes sour water production hydrogen sulfide, has realized storing of under-stream period hydrogen sulfide.Concrete first shut-down and on-stream time and needs store the amount of sour water, depend on benefit sulfur content and the sour water sulphur content of hydrogenation of tar device needs, and this respect need to finally calculate solution according to coal tar hydrogenating unit scale, the catalytic amount that fills.
Going into operation first of coal tar hydrogenating new device, install desirablely without sulphur, and some start and use vulcanizing agent DMDS to need buying.After to reactive system, injecting vulcanizing agent DMDS, vulcanizing agent generates hydrogen sulfide with hydrogen, hydrogen sulfide produces water when on catalyzer, the oxidation state precious metal reacts, this strand of water dissolution partial vulcanization hydrogen can progressively be set up the working of single tower stripping tower, to start as early as possible the hydrogen sulfide compressor, reclaim hydrogen sulfide, fill into to the hydrogenation of tar system.
The invention has the beneficial effects as follows:
1, hydrogen sulfide is injected into to reactor inlet with compressor, directly make up reaction required, avoid this part high purity hydrogen sulfide to flow in high-pressure separator, circulating hydrogen compressor, high pressure heat exchanger, process furnace etc., reduce as possible its corrosion to the high-tension apparatus pipeline.
2, by by the hydrogen sulfide compression and back coal tar hydrogenating unit of follow-up workshop section reaction high-pressure section, maintaining the concentration of hydrogen sulfide of recycle hydrogen system, can save the notes sulphur agent DMDS of a large amount of costlinesses, is the device create beneficial result of economizing on the use of funds.
3, after the DMDS injected system with hydrogen reaction, in the time of consumption systems hydrogen, also produce a large amount of methane.Methane gas has reduced hydrogen purity in the recycle hydrogen system, increases the power consumption of circulating hydrogen compressor, unfavorable to hydrogenation reaction.And injection hydrogen sulfide directly makes up reaction required, consumption systems hydrogen, additionally do not carry impurity, therefore annotates hydrogen sulfide more more advantageous than annotating vulcanizing agent DMDS.
Claims (2)
1. the benefit sulphur technique of coal tar hydrogenating unit, is characterized in that: by hydrogen sulfide in single tower stripping return tank of top of the tower, be compressed to the coal tar hydrogenating reactor inlet, to keep recycle hydrogen system hydrogen sulfide content 500-1000ppm left and right.
2. benefit sulphur technique as claimed in claim 1, it is characterized in that: by single tower stripping sour water storage tank, by adjusting single tower stripper plant and coal tar hydrogenating unit start-stop work step order, for coal tar hydrogenating unit go into operation (first non-) catalyst vulcanization hydrogen sulfide is provided.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103743406A CN103436285A (en) | 2013-08-26 | 2013-08-26 | Sulphur supplement process for coal tar hydrogenation device |
| CN201410077469.5A CN103911176A (en) | 2013-08-26 | 2014-03-01 | Sulfur supplementing process for oil product hydrogenation apparatus |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103743406A CN103436285A (en) | 2013-08-26 | 2013-08-26 | Sulphur supplement process for coal tar hydrogenation device |
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| CN103436285A true CN103436285A (en) | 2013-12-11 |
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| CN2013103743406A Pending CN103436285A (en) | 2013-08-26 | 2013-08-26 | Sulphur supplement process for coal tar hydrogenation device |
| CN201410077469.5A Pending CN103911176A (en) | 2013-08-26 | 2014-03-01 | Sulfur supplementing process for oil product hydrogenation apparatus |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927904A (en) * | 2014-05-20 | 2015-09-23 | 王荣超 | Hydrotreating sulfur supplementing method |
| CN106047403A (en) * | 2016-07-13 | 2016-10-26 | 神华集团有限责任公司 | Method and device for injecting sulfur supplementing agent into hydrogenation reactor in direct coal liquefaction process |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104946300A (en) * | 2015-05-28 | 2015-09-30 | 王荣超 | Sulfur supplement device for hydrotreatment |
| CN105344293B (en) * | 2015-11-28 | 2018-06-22 | 王荣超 | The hydrogen sulfide compression method and device of hydrotreating |
| CN108441256A (en) * | 2018-03-06 | 2018-08-24 | 国家能源投资集团有限责任公司 | Benefit sulphur method and device in hydroprocessing processes |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087933A (en) * | 1993-12-27 | 1994-06-15 | 中国石化洛阳石油化工工程公司 | Sulfur suppelementary agent in use for hydrogenation processing |
| CN102329640B (en) * | 2010-07-13 | 2014-08-20 | 中国石油化工股份有限公司 | Integrated hydrocracking method |
| CN103059913B (en) * | 2011-10-21 | 2015-09-02 | 中国石油化工股份有限公司 | The Startup presulfurization method of hydrogenation catalyst |
| CN102899071B (en) * | 2012-10-08 | 2014-12-24 | 西北大学 | Coal tar hydrogenation method |
-
2013
- 2013-08-26 CN CN2013103743406A patent/CN103436285A/en active Pending
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- 2014-03-01 CN CN201410077469.5A patent/CN103911176A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927904A (en) * | 2014-05-20 | 2015-09-23 | 王荣超 | Hydrotreating sulfur supplementing method |
| CN106047403A (en) * | 2016-07-13 | 2016-10-26 | 神华集团有限责任公司 | Method and device for injecting sulfur supplementing agent into hydrogenation reactor in direct coal liquefaction process |
| CN106047403B (en) * | 2016-07-13 | 2018-04-03 | 神华集团有限责任公司 | The method for implanting and injection device of hydrogenation reactor sulfur supplementary agent in a kind of direct coal liquefaction process |
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|---|---|
| CN103911176A (en) | 2014-07-09 |
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Application publication date: 20131211 |