CN104117277A - Recovering method of acid waste gas in crude benzene hydrofining project - Google Patents
Recovering method of acid waste gas in crude benzene hydrofining project Download PDFInfo
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- CN104117277A CN104117277A CN201410312583.1A CN201410312583A CN104117277A CN 104117277 A CN104117277 A CN 104117277A CN 201410312583 A CN201410312583 A CN 201410312583A CN 104117277 A CN104117277 A CN 104117277A
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Abstract
A recovering method of acid waste gas in a crude benzene hydrofining project is disclosed. Hydrogen sulfide gas is fed into an absorbing kettle with a special distributer after the hydrogen sulfide gas is subjected to ammonia washing for purification by a washer. Liquid sodium hydroxide is adopted to absorb the hydrogen sulfide gas. The method is characterized in that: the reaction time of the hydrogen sulfide and the sodium hydroxide is accelerated under the action of a novel catalyst (BAS) so as to avoid production of carbonate and other byproducts, thus obtaining a high-purity sodium hydrosulfide liquid product, the quality indexes of the product exceed the indexes of the GB23937-2009 standard, the content is 32-38%, the content of the carbonate is lower than 0.8%, and the content of iron is lower than 20 ppm. The method is advantageous in that: the disadvantages of the prior art are overcome by the method, the high-purity sodium hydrosulfide liquid product is obtained, and the method is environmental friendly. The method has characteristics of low energy consumption in production processes, complete hydrogen sulfide utilization, easily controlled production processes, and environment protection, and is suitable for popularization and application.
Description
Technical field
The invention belongs to chemical technology field, relate to the recovery method of the refining entry means acid waste gas of a kind of crude benzole hydrogenation.
Background technology
The recycling technology of sour gas hydrogen sulfide in crude benzole hydrogenation commercial benzene, toluene, xylene production technique now, what mainly adopt is that burning and exhausting method, claus oven are produced sulfur method or reclaimed sodium hydrosulfide.
Technique major defect is now: 1, the equal exhaust emission gaseous sulfur dioxide of torch burning method and Recovered sulphur method.2, hydrogen sulfide gas is recycled not exclusively, and utilization rate is low, and environment is had to pollution.3, spray column circulated sprinkling absorbing hydrogen sulphide method, yield is low, and hydrogen sulfide absorption utilization is incomplete, the poor content of liquid sulfur sodium hydride product quality low (general 15-20%) of its recovery, and also impurity is many, the scope of application is restricted.For example Shijiazhuang, Hebei, Tangshan, Xingtai, Taiyuan, Shanxi, Xiaoyi, Xuzhou, Zhenjiang, Heze City, Shandong Province, Binzhou, what the clumsy hydrofinishing process units on the ground such as Northern Huaihe River Anhui, Anqing all used the recycling of sour gas hydrogen sulfide is above several method.(1) adopt hydrogen sulfide is sent into torch burning method processing hydrogen sulfide, a large amount of exhaust emission gaseous sulfur dioxide, taking Binzhou, Shandong, the crude benzole hydrogenation device of 100,000 tons/year is as example, and device year produces 298 tons, hydrogen sulfide, adopt the processing of torch burning method, 595 tons/year of discharge sulfur dioxide.(2) by hydrogen sulfide Recovered sulphur, only have 95-98% as its recovery process hydrogen sulfide utilization rates of enterprise such as Shijiazhuang, Hebei, Xingtai, still have the hydrogen sulfide of 2-5% to be discharged in atmosphere with the form of sulfur dioxide and hydrogen sulfide, cause the harm to environment.(3) with hydrogen sulfide withdrawal liquid NaHS.Most enterprises such as such as Dezhou, Shandong, Lianyungang of Jiangsu, Nantong, its production technology is secondary or three grades of spray columns mostly, the general use of tower diameter is 0.8-1.2m, high 3.5m, use the alkali lye of 15-20% to carry out spray-absorption, gas reacts with the alkali lye counter current contacting from tower top spray at Ta Nei, generates NaHS.The product quality of this kind of explained hereafter is poor, and content is low, and the impurity such as special carbonate containing, iron are too many, and only one of iron index just exceedes 150PPm, market cheaper, and average 400 yuan/ton, range of application is too narrow.And hydrogen sulfide utilization rate is too low, contaminated environment, equipment operation energy consumption is high, and the easy Crystallization Plugging pipeline of production process, valve, and operating difficulties, pollutes and wastes.
Summary of the invention
In order to overcome the defect existing in prior art, the present invention proposes in a kind of production process, energy consumption is low, be easy to control, product quality is high and hydrogen sulfide utilizes the recovery method of the refining entry means acid waste gas of crude benzole hydrogenation completely.
Object of the present invention is in particular in the following aspects:
(1) air conservation, hydrogen sulfide gas recovery process does not produce dusty gas sulfur dioxide.
(2) overcome spray column and absorb shortcoming, improve hydrogen sulfide utilization rate, can reach 99.9%.
(3) produce the NaHS product that content is high, purity is high and the scope of application is wide.
(4) applied range; be applicable to the process units such as clumsy hydrogenation, petroleum naphtha hydrogenation, lube base oil hydro-upgrading, Coal Chemical Industry coal tar hydrogenating, catalysis oil refining, carbolineum lighting, pesticide chemical, petroleum additive, peptizer, medicine intermediate; effectively solve its hydrogen sulfide waste gas; turn waste into wealth; be recycled into high-purity NaHS product, protection of the environment.
This new technique key is the deamination of hydrogen sulfide mix waste gas to purify and new catalytic absorption technique technology.Hydrogen sulfide gas is after washer is washed ammonia purification, enter the absorption kettle with special distributor, adopt liquid caustic soda absorbing hydrogen sulphide gas, the crucial reaction time of accelerating hydrogen sulfide and caustic soda under the effect of new catalyst (BAS), avoid the generation of the side reaction things such as carbonate, thereby obtain high-purity NaHS fluid product, quality index exceedes GB23937-2009 standard index, content reaches 32-38%, carbonate is lower than 0.8%, iron is to have overcome now general technique shortcoming lower than the advanced part of 20PPm, obtain quality product high-purity NaHS fluid product, protection of the environment.
Its technical scheme is as follows:
A recovery method for the refining entry means acid waste gas of crude benzole hydrogenation, comprises the following steps:
1) in advance 32-38% liquid caustic soda is added respectively after accurate-metering in three grades of absorption kettle A/B/C, open the hydrogen sulfide imported valve on absorption kettle top, first gas enter in absorption kettle A, through in still porous distributor distribute after with caustic soda hybrid reaction, the tail gas of absorption kettle A enters in absorption kettle B again and continues to react, the tail gas of absorption kettle B enters absorption kettle C again and again reacts, the tail gas of absorption kettle C enters surge tank, drain into tail gas water sealed tank through vavuum pump, then remove total tail gas pipe network, hydrogen sulfide utilization rate reaches 99.9%.Under the negative pressure state of course of reaction about vacuum is 0.03mpa, carry out (also can adopt malleation absorption pattern according to concrete technology situation), every its absorption kettle of cover absorption plant is three grades of series connection and uses, guarantee that tail gas absorbs completely, in the time that absorption kettle A temperature reaches 40 DEG C, add catalyst B BS2.5 kilogram to absorption kettle A, press 0.4-0.5 kg/ton caustic soda and calculate addition, insulation reaction, prevents crystallization;
2) when absorption kettle A temperature reaches 80 DEG C, gas is switched to three grades of absorption plants of another group, then opens the sample cock of absorption kettle A, take out sample 20ml left and right, send laboratory detect, detect qualified after by the NaHS product of A still with pumping out to holding vessel; Defective if NaHS is analyzed, carry out again sample analysis after will continuing to absorb certain hour.
3) product conveying is complete, closes the dispensing valve of absorption kettle A, and the alkali lye of absorption kettle B/C is proceeded in absorption kettle A, then absorption kettle B/C is added respectively again again to the caustic soda of new specified quantity.Carry out the production of next round, by that analogy, circulation is produced again.
Beneficial effect of the present invention is: the sour gas deamination purification after cure hydrogen that the present invention adopts novel absorption process that crude benzole hydrogenation device is discharged reacts the method that generates NaHS with caustic soda, makes clumsy hydrofinishing process units hydrogen sulfide waste gas administer operation and does not produce dusty gas sulfur dioxide.Protection of the environment, the hydrogen sulfide rate of recovery can reach 99.9%, reclaims high-purity 32-38% NaHS product.This technology applied range; be applicable to the process units such as crude benzole hydrogenation, petroleum naphtha hydrogenation, Coal Chemical Industry coal tar hydrogenating, catalysis oil refining, lube base oil hydro-upgrading, carbolineum lighting, petroleum additive, pesticide chemical, peptizer, medicine intermediate, dressing agent; effectively solve its hydrogen sulfide gas pollution problem; turn waste into wealth, protection of the environment.
Detailed description of the invention
Below in conjunction with detailed description of the invention, technical scheme of the present invention is described in more detail.
A recovery method for the refining entry means acid waste gas of crude benzole hydrogenation, comprises the following steps:
1) in advance 32-38% liquid caustic soda is added respectively after accurate-metering in three grades of absorption kettle A/B/C, open the hydrogen sulfide imported valve on absorption kettle top, after first gas enter in absorption kettle A, in still, porous distributor distributes and caustic soda hybrid reaction, the tail gas of absorption kettle A enters in absorption kettle B again and continues to react, the tail gas of absorption kettle B enters absorption kettle C again and again reacts, the tail gas of absorption kettle C enters surge tank, drain into tail gas water sealed tank through vavuum pump, then remove total tail gas pipe network, hydrogen sulfide utilization rate reaches 99.9.Under the negative pressure state of course of reaction about vacuum is 0.03mpa, carry out (also can adopt malleation absorption pattern according to process condition), every cover absorption plant absorption kettle is three grades of series connection and uses, guarantee that tail gas absorbs completely, in the time that absorption kettle A temperature reaches 40 DEG C, add catalyst B BS2.5 kilogram to absorption kettle A, press 0.4-0.5 kg/ton caustic soda and calculate addition, insulation reaction, prevents crystallization;
2) when absorption kettle A temperature reaches 80 DEG C, gas is switched to another group absorption kettle, then opens the sample cock of absorption kettle A, take out sample 20ml left and right, send laboratory to detect, detect qualified after by the NaHS product of A still with pumping out to holding vessel; Defective if NaHS is analyzed, again carry out sample analysis after will continuing again to absorb certain hour.
3) product conveying is complete, closes the dispensing valve of absorption kettle A, and the alkali lye of absorption kettle B/C is proceeded in absorption kettle A, then absorption kettle B/C is added respectively again to the caustic soda of new specified quantity again, then carries out the production of next round, and by that analogy, circulation is produced.
The technology of the present invention key is using method, use amount and the joining day of new catalyst BAS, in the reaction time that regulates hydrogen sulfide and caustic soda, suppresses the generation of the side reaction things such as carbonate with this.Disc type distributor special in absorption kettle distributes respond well, gas-liquid contact is even, be beneficial to reaction, key is non-crystallizable obstruction, the problem such as crystallization, obstruction valve pipe that has overcome old technique, has improved reaction yield, yield >=99.9%, thereby obtain high-purity NaHS fluid product, quality index exceedes GB23937-2009 standard index.Main content reaches 32-38%, and carbonate is lower than 0.8%, and iron is lower than 20PPm.Advanced part is to have overcome now general technique shortcoming, obtains quality product high-purity NaHS fluid product, protection of the environment.
1, the present invention and other technique comparisons, this technique does not produce secondary pollution.
2, improve hydrogen sulfide utilization rate.
3, the NaHS purity of manufacturing is high, without purifying and just can be widely used in medication chemistry, daily use chemicals industry again.Specific experiment data are as shown in table 1.
Table 1 (according to 150,000/year ton crude benzole hydrogenation refining plant)
The above; it is only preferably detailed description of the invention of the present invention; protection scope of the present invention is not limited to this; any be familiar with those skilled in the art the present invention disclose technical scope in, the simple change of the technical scheme that can obtain apparently or equivalence replace all fall within the scope of protection of the present invention.
Claims (2)
1. a recovery method for the refining entry means acid waste gas of crude benzole hydrogenation, is characterized in that, comprises the following steps:
1) in advance 32-38% liquid caustic soda is added respectively after accurate-metering in three grades of absorption kettle A/B/C, open the hydrogen sulfide imported valve on absorption kettle top, after gas enters in absorption kettle A, distribute and caustic soda hybrid reaction through porous distributor, the tail gas of absorption kettle A enters in absorption kettle B again and continues to react, the tail gas of absorption kettle B enters absorption kettle C again and again reacts, the tail gas of absorption kettle C enters surge tank, drain into tail gas tank through vavuum pump, then remove total tail gas pipe network, hydrogen sulfide utilization rate reaches 99.9; Under the negative pressure state that course of reaction is 0.03mpa in vacuum, carry out, every cover absorption plant absorption kettle is three grades of series connection, switches and uses, and guarantees that tail gas absorbs completely, ensures to produce normal operation; In the time that absorption kettle A temperature reaches 40 DEG C, add catalyst B BS2.5 kilogram to absorption kettle A, calculate addition by 0.4-0.5 kg/ton caustic soda, insulation reaction, prevents crystallization;
2), when absorption kettle A temperature reaches 80 DEG C, gas is switched to another group absorption plant; Then open the sample cock of absorption kettle A, take out sample 20ml left and right, send laboratory to detect, detect qualified after by the NaHS product of A still with pumping out to holding vessel, if it is defective to detect analysis NaHS, need to continue to carry out again sample analysis after absorption certain hour;
3) product conveying is complete, closes the dispensing valve of absorption kettle A, and the alkali lye of absorption kettle B/C is proceeded in absorption kettle A, then absorption kettle B/C is added respectively again again to the caustic soda of new specified quantity; Carry out the production of next round, by that analogy, circulation is produced again.
2. the recovery method of the refining entry means acid waste gas of crude benzole hydrogenation according to claim 1, is characterized in that,
Described absorption plant comprises the hydrogen sulfide retracting device of the compositions such as the vavuum pump of washer, separator, surge tank, measuring tank, three grades of series connection alkali absorption kettles, tail gas tank and necessity, in absorption kettle, be provided with and insert liquid pipe and suitable gas distributor, divide negative pressure absorbing and malleation to absorb two kinds of absorption patterns, under uniform temperature control, complete separation, the recovery of hydrogen sulfide gas, obtain high-quality NaHS product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107019994A (en) * | 2017-04-27 | 2017-08-08 | 唐山华熠实业股份有限公司 | The processing method and system of crude benzole hydrogenation sulfurous gas |
| CN108636323A (en) * | 2018-06-06 | 2018-10-12 | 南京曙光精细化工有限公司 | Polysulfide silanes coupling agent process units |
| CN109316817A (en) * | 2018-12-08 | 2019-02-12 | 大连福佳·大化石油化工有限公司 | NaHS entrucking filtration cycle system |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3130007A (en) * | 1961-05-12 | 1964-04-21 | Union Carbide Corp | Crystalline zeolite y |
| GB1506429A (en) * | 1975-05-13 | 1978-04-05 | Union Carbide Corp | Catalyst for hydrocarbon processes and process for preparing same |
| US4645750A (en) * | 1984-08-21 | 1987-02-24 | Union Caride Corporation | Urea rejuvenation of catalysts |
| US5538925A (en) * | 1995-08-14 | 1996-07-23 | The United States Of America As Represented By The Secretary Of The Navy | Si3 N4 reinforced monoclinic BaO.Al2 O3 2S2 and SrO.Al2 O3.2SiO2 ceramic composites |
| US6039929A (en) * | 1997-12-15 | 2000-03-21 | The United States Of America As Represented By The Secretary Of The Navy | Synthesis of monoclinic celsian |
| CN101489950A (en) * | 2006-07-21 | 2009-07-22 | 陶氏环球技术公司 | Imroved diesel particulate filter |
| CN103270142A (en) * | 2010-12-23 | 2013-08-28 | 道达尔炼油与销售部 | Process for preparing an industrial hydroconversion catalyst, catalyst thus obtained and use thereof in a hydroconversion process |
-
2014
- 2014-07-03 CN CN201410312583.1A patent/CN104117277A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3130007A (en) * | 1961-05-12 | 1964-04-21 | Union Carbide Corp | Crystalline zeolite y |
| GB1506429A (en) * | 1975-05-13 | 1978-04-05 | Union Carbide Corp | Catalyst for hydrocarbon processes and process for preparing same |
| US4645750A (en) * | 1984-08-21 | 1987-02-24 | Union Caride Corporation | Urea rejuvenation of catalysts |
| US5538925A (en) * | 1995-08-14 | 1996-07-23 | The United States Of America As Represented By The Secretary Of The Navy | Si3 N4 reinforced monoclinic BaO.Al2 O3 2S2 and SrO.Al2 O3.2SiO2 ceramic composites |
| US6039929A (en) * | 1997-12-15 | 2000-03-21 | The United States Of America As Represented By The Secretary Of The Navy | Synthesis of monoclinic celsian |
| CN101489950A (en) * | 2006-07-21 | 2009-07-22 | 陶氏环球技术公司 | Imroved diesel particulate filter |
| CN103270142A (en) * | 2010-12-23 | 2013-08-28 | 道达尔炼油与销售部 | Process for preparing an industrial hydroconversion catalyst, catalyst thus obtained and use thereof in a hydroconversion process |
Non-Patent Citations (1)
| Title |
|---|
| 虞剑秋等: "改良BBs法评价聚氨醋发泡催化剂", 《高分子材料科学与工程》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107019994A (en) * | 2017-04-27 | 2017-08-08 | 唐山华熠实业股份有限公司 | The processing method and system of crude benzole hydrogenation sulfurous gas |
| CN107019994B (en) * | 2017-04-27 | 2019-05-24 | 唐山华熠实业股份有限公司 | The processing method and system of crude benzole hydrogenation sulfurous gas |
| CN108636323A (en) * | 2018-06-06 | 2018-10-12 | 南京曙光精细化工有限公司 | Polysulfide silanes coupling agent process units |
| CN108636323B (en) * | 2018-06-06 | 2024-02-20 | 南京曙光新材料有限公司 | Polysulfide silane coupling agent production device |
| CN109316817A (en) * | 2018-12-08 | 2019-02-12 | 大连福佳·大化石油化工有限公司 | NaHS entrucking filtration cycle system |
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Application publication date: 20141029 |