CN1429764A - CO isothermal sulfur resistant conversion process - Google Patents
CO isothermal sulfur resistant conversion process Download PDFInfo
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- CN1429764A CN1429764A CN 01142861 CN01142861A CN1429764A CN 1429764 A CN1429764 A CN 1429764A CN 01142861 CN01142861 CN 01142861 CN 01142861 A CN01142861 A CN 01142861A CN 1429764 A CN1429764 A CN 1429764A
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Abstract
A S-resistant isothermal conversion process for CO features that CO reacts on water vapour to generate H2 and CO2 used for preparing synthetic ammonia gas, H2, and synthetic carbonyl gas. The reactive heat is removed by water-steam and/or other circulating medium. The reaction temp. can be controlled by regulating the pressure and/or flow of circulating medium. Its advantages are simple operation, high activity and long service life of catalyst, and low dosage of catalyst.
Description
Technical field
The present invention relates to a kind of isothermal sulfur-tolerant conversion process that carbon monoxide and steam reaction are produced hydrogen and carbonic acid gas that is used for.
Background technology
The CO transformationreation plays an important role in synthetic ammonia, oxo-synthesis gas and town gas engineering, and the energy consumption of conversion section is occupied suitable ratio in whole energy consumption.In recent years, the conversion type of furnace, conversion process are optimized, transform, when reducing steam consumption, the high and low position heat energy of fully recycling transformation system will be one of energy-saving and cost-reducing important channel of synthesis ammonia plant.
In traditional CO sulfur resistant conversion process, reaction is carried out in the common response device, is in adiabatic condition, has following drawback: move because the most of catalyzer in the beds is in higher temperature, its life-span must be affected; Temperature of reactor is difficult to control, occurs fluctuation easily; Catalyst vulcanization process complexity, and be easy to generate the sulfuration overtemperature; Need extra start up boilers, so as to catalyzer heat up, sulfuration etc.; Owing to be subjected to the influence of thermal insulation warming, reactor outlet CO concentration is subjected to the equilibrated restriction, is difficult to the level that reaches lower; Be subjected to the restriction of factors such as catalyst shape, type of feed, gas distribution is inhomogeneous; The shift converter volume is big, the flow process complexity.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, a kind of new CO sulfur resistant conversion process is provided.Compared with prior art, this technology has characteristics such as temperature operation is steady, control is simple, easy to operate, and flow process is short, and outlet CO minimum content is low.
In order to achieve the above object, technology of the present invention mainly is made up of reactor assembly and heat recuperation-temperature controlling system.
Reactor assembly of the present invention can be an independently reactor, also can adopt a plurality of reactors in series, the in parallel use.Catalyzer both can be seated in a series of tube banks of shell and tube reactor, also can directly be seated in the tower tank reactor of built-in heat exchange coil.The purpose that adopts this special reaction device structure is the heat that produces in the CO transformationreation process in order to remove fast, thereby reaches isothermal purpose.The heat-transfer medium that is used to remove reaction heat of the present invention mainly is a water, promptly so-called saturation water-steam system.Certainly, also can adopt other similar material, its objective is in reaction process and remove reaction heat fast.
For shell and tube reactor, catalyst loading is used for fluming water-steam and/or other heat-transfer medium between pipe in a series of tube banks of shell and tube reactor.When reaction process was stablized, the water level of bottom also tended towards stability between the pipe of reactor, and produced in a large number when hot when reaction, and the water of bottom inlet becomes water vapor fast, formation gas-liquid two-phase flow body in reactor assembly.Because the carburetion of saturation water, make the heat that produces in the reaction process to remove by the mode of steam.The band that leaves reactor press steam through pipe-line transportation in the drum of reactor outside, part is as heat recuperation, another part comes back to shift-converter after by condensation.Therefore, can reach isothermal purpose by the temperature that the internal circulating load or the pressure of steam regulation-saturation water system are regulated beds.Reduce as saturated water amount, can suitably be complemented in the saturator, little to the temperature effect of reactor assembly.There is not strict restriction for size, quantity and the length of tubulation, can be according to producing decisions such as load, process gas composition, but must be able to satisfy the requirement of catalyzer.In addition, the heat-transfer effect of tubulation will be got well, so that reaction heat in time can be delivered between pipe.
In the technology of the present invention, catalyzer also can directly be seated in the tower tank reactor, at this moment, is provided with an amount of heat exchange coil in the beds of reactor, and this coil pipe is embedded in the beds fully, and mobile is a heat-conducting medium in the pipe.Heat-conducting medium can be any can the mobile material, but the fluidic thermal capacitance should be enough big, so that can utilize effective flow just reaction heat in time can be shifted out beds in the unit time.As adopting this catalyst loading pattern, then above-mentioned drum part should correspondingly change heat-transfer medium cycling element and heat exchange unit into.The heat-transfer medium cycling element comprises heat-transfer medium and impels its round-robin handling equipment that in heat exchange unit, the contained reaction heat of heat-transfer medium is removed.
In the isothermal sulfur-tolerant conversion process of the present invention, reactor can be one section shift-converter, also can increase to 2～3 sections according to actual needs.
Isothermal sulfur-tolerant conversion process of the present invention, can be different the raw gas that produces of gas-making process as raw material.Typical process feed gas comprises: the synthetic gas that the residual oil partial oxidation process produces; The synthetic gas that coal water slurry gasification technology produces; The synthetic gas that the coal gasification method produces etc.Wherein, be particularly suitable for handling the higher synthetic gas of CO content, for example the high CO synthetic gas of producing by coal dust gasification.Under normal operational condition, butt CO forms can reach 75% even higher.For the lower low temperature shift process of CO content, the present invention is particularly suitable also, and the minimum outlet of shift converter this moment CO content can reach 1%
In the technology of the present invention, the reactor operating temperature range is controlled at 180～450 ℃, pressure range between 1～10Mpa, and process gas sulphur content＞0.01%v/v, water to steam ratio are 0.4～1.8.
Outstanding feature of the present invention is:
(1) adopt vapor pressure, heat-conducting medium flow to come the conditioned reaction temperature, production control and operate simple and flexible more;
(2) catalyzer is in comparatively in the demulcent isothermal reaction process, can prolong catalyzer work-ing life.
(3) catalyst vulcanization is simple, rapidly and do not have overheated danger, is difficult for producing the sulfuration overtemperature;
(4) the used vapour heat directly heats up to catalyzer, does not need extra start up boilers;
(5) can eliminate the restriction of the balance factor of the generation by thermal insulation to outlet CO minimum concentration, under identical condition, outlet CO content is starkly lower than traditional sulfur resistant conversion process.
Description of drawings
Fig. 1 is traditional sulfur resistant conversion process general flow chart.
Fig. 2 is an isothermal sulfur-tolerant conversion process sketch of the present invention.
Fig. 3 is the sketch of catalyst loading pattern 1 of the present invention.
Fig. 4 is the sketch of catalyst loading pattern 2 of the present invention.
General flow chart of the present invention as shown in Figure 2.Fluid in the pipeline 1 is the raw gas from gas making workshop section, and this coal gas passes through impurity such as washing tower 2 laggard one-step removal carbon blacks, and water/dry gas is adjusted to suitable level, and phlegma wherein enters the ground hyposulculus through pipeline 22.The process gas that goes out washing tower 2 obtains heating in gas heater 6 behind the outlet line 3 of washing tower 2 and pipeline 5, enter isothermal reactor 8 through the process gas of preheating through pipeline 7.Transformationreation is carried out in the tubulation tube bank that the isothermal sulfur-tolerant conversion catalyzer is housed.In case of necessity, this process gas can enter another unit such as temperature shift reaction such as grade.In isothermal reactor 8, the process gas and the water-steam between pipe of restraining by tubulation carry out the noncontact heat exchange, and reaction heat is restrained through tubulation and taken away by heat-transfer medium.
Portion water between reactor tube is vaporized owing to having absorbed a large amount of reaction heat, and pressure raises and enters respectively in the water- steam drum 10,16 that is located at separately outside the reactor through pipeline 9,15.In described drum 10,16, band presses steam to be transported to suitable steam pipe system through steam- pipe 11,17 respectively, so that further utilize.What of reaction heat vapor pressure in the drum 10 depend primarily on, and also is subjected to the restriction of its flow simultaneously.Saturation water in the drum 10,16 is back between the pipe of reactor by pipeline 12,18 respectively, and the process gas that goes out reactor 8 enters in the reactor 14 through piping 13, enters next workshop section through piping 19 then.The thermal source of gas heater 6 is carried by pipeline 20 and 21.
When the transformationreation temperature raises, can control by flow or the pressure of regulating water-steam.When owing to a large amount of delivery of steam when pipe network makes that the water yield reduces, it is additional pass through pipeline 23 (24 etc.).
Can come reactor assembly input N by pipeline 4
2Or in system, add steam.Particularly use latter stage, be necessary by normally carrying out that the mode of replenishing steam guarantees to react when catalyzer.In reactor assembly, feed N
2Mainly be to be used for purposes such as purging.
The process gas that gas heater 6 is mainly used in entering first shift converter heats, and is minimum with water of condensation content in the process gas that guarantees to enter reactor.The thermal source of gas heater 6 can be a steam, also can be the process gas of heat.
Fig. 3 is a catalyst loading pattern 1 of the present invention.In the suitable reactor of a volume, a series of tube banks that distributing equably, the quantity of tube bank and length are determined by factors such as conversion load and reaction conditionss.Catalyst loading is in tubulation, and mobile is the water-steam mixture two phase flow in the space between pipe.When reaction process was stablized, the water level of bottom also tended towards stability between reactor tube, and produced in a large number when hot when reaction, and unnecessary heat can be vaporized rapidly because of the water between pipe and is pulled away.Thereby the bottom between reactor tube, should keep the suitably water of height, so that the heat that produces in the reaction process in time can be removed.As mentioned above, can and or 24 replenish suitable water by pipeline 23.
Fig. 4 is a catalyst loading pattern 2 of the present invention.Reactor among the figure is similar to the reactor that is adopted in traditional sulfur resistant conversion process.Different is that one or one group of coil pipe that supplies heat exchange to use have been placed by portion within it.This coil pipe is embedded in the beds fully, and circulation is heat-conducting medium in the pipe.As adopt catalyst loading pattern shown in Figure 4, corresponding heat-transfer medium cycling element and the heat exchange unit of changing into of the drum part among Fig. 2.This cycling element comprises heat-transfer medium and impels its round-robin handling equipment that in described heat exchange unit, the contained reaction heat of heat-transfer medium is removed.
Embodiment
For characteristics of the present invention are described better, be described further below in conjunction with embodiment, but the present invention is not limited to following embodiment.
Embodiment 1
At pressure 4.0MPa, dry gas air speed 3000hr
-1, water/dry gas ratio is 1.2, inlet gas is formed (butt) and is: CO45.5%, CO
22.5%, H
2S3000ppm, CH
40.4%, surplus is H
2Condition under, the situations such as reactor outlet CO of isothermal sulfur-tolerant conversion process are investigated.And compare with traditional sulfur resistant conversion process, the results are shown in table 1.Tradition conversion appreciation condition is an adiabatic reactor, and conversion conditions such as catalyst loading are identical with isothermal process of the present invention.
Traditional sulfur resistant conversion process of table 1 and isothermal sulfur-tolerant conversion process are relatively
| Sequence number | The tradition sulfur resistant conversion process | Isothermal sulfur-tolerant conversion process | |||
| Temperature in (℃) | Temperature out (℃) | CO interconversion rate (%) | Temperature of reaction (℃) | CO interconversion rate (%) | |
| ??1 | ????180 | ????313 | ????91.1 | ????180 | ????91.9 |
| ??2 | ????250 | ????408 | ????96.4 | ????250 | ????96.7 |
| ??3 | ????285 | ????438 | ????94.2 | ????285 | ????95.6 |
| ??4 | ????300 | ????449 | ????91.8 | ????300 | ????94.5 |
| ??5 | ????450 | ????495 | ????88.5 | ????450 | ????91.3 |
Under identical entry condition, the active comparing result of 1000 hours front and back of catalyzer operation is listed in table 2.The activity rating condition is: pressure 4.0MPa, dry gas air speed 3000hr
-1, water/dry gas 1.2, inlet gas is formed (butt): CO45.5%, CO
22.5%, H
2S3000ppm, CH
40.4%, surplus is H
2Tradition conversion appreciation condition is an adiabatic reactor, and conversion conditions such as catalyst loading are identical with isothermal process of the present invention.
Catalyst life relatively under the identical entry condition of table 2
| Temperature in (℃) | Hot(test)-spot temperature (℃) | Temperature out (℃) | CO interconversion rate (%) | ||
| Raw catalyst | After 1000 hours | ||||
| Traditional technology | ???285 | ???435 | ????408 | ????94.2 | ????90.5 |
| Isothermal process | ???285 | ???286.5 | ????285 | ????95.6 | ????95.1 |
Under identical entry condition, the active comparing result of catalyzer under high CO condition listed in table 3.The activity rating condition is: pressure 4.0MPa, dry gas air speed 3000hr
-1, water/dry gas 1.2.Inlet gas is formed (butt): CO65.5%, CO
23.5%, H
2S3000ppm, CH
40.4%, surplus is H
2Tradition conversion appreciation condition is an adiabatic reactor, and conversion conditions such as catalyst loading are identical with isothermal process of the present invention.
The contrast of table 3 under high CO entry condition
| Sequence number | The tradition sulfur resistant conversion process | Isothermal sulfur-tolerant conversion process | |||
| Temperature in (℃) | Temperature out (℃) | CO interconversion rate (%) | Temperature of reaction (℃) | CO interconversion rate (%) | |
| ????1 | ????250 | ????452 | ????91.2 | ????250 | ????95.9 |
| ????2 | ????285 | ????468 | ????89.4 | ????285 | ????94.8 |
| ????3 | ????300 | ????489 | ????87.1 | ????300 | ????93.7 |
Embodiment 4
Under identical entry condition, the active comparing result of catalyzer under low inlet CO content condition sees Table 4.The activity rating condition is: catalyzer loading amount 100 grams, pressure 4.0MPa, dry gas air speed 3000hr
-1, water/dry gas 1.2.Inlet gas is formed (butt): CO1%, CO
238%, H
2S3000ppm, CH
40.4%, surplus is H
2
The contrast of table 4 under low CO entry condition
| Sequence number | The tradition sulfur resistant conversion process | Isothermal sulfur-tolerant conversion process | |||
| Temperature in (℃) | Temperature out (℃) | CO interconversion rate (%) | Temperature of reaction (℃) | CO interconversion rate (%) | |
| ??1 | ????250 | ????254 | ????69.1 | ????250 | ????69.9 |
| ??2 | ????285 | ????291 | ????67.9 | ????285 | ????68.6 |
| ??3 | ????300 | ????307 | ????66.7 | ????300 | ????66.8 |
Under the identical entry condition, isothermal process of the present invention and the traditional technology comprehensive contrast situation on large-scale plant is listed in table 5.Pressure 4.0MPa, total dry gas volumetric flow rate: 110000m
3/ hour, water/dry gas 1.2,285 ℃ of temperature ins.Inlet gas is formed (butt): CO45.5%, CO
22.5%, H
2S3000ppm, CH
40.4%, surplus is H
2Tradition conversion appreciation condition is an adiabatic reactor, and conversion conditions such as catalyst loading are identical with isothermal process of the present invention.Catalyst loading in this example is in shell and tube reactor.
Two kinds of technology contrasts on large-scale plant of table 5
| The catalyzer loading amount, m 3 | The CO outlet, % | Temperature out, ℃ | The CO transformation efficiency, % | |
| Traditional technology | ????10 | ????20.859 | ????364.89 | ????44.80928 |
| ????15 | ????16.3455 | ????391.16 | ????55.07375 | |
| ????20 | ????13.5745 | ????409.34 | ????61.77965 | |
| ????25 | ????8.347 | ????427.15 | ????75.36429 | |
| ????30 | ????6.3155 | ????433.61 | ????81.00397 | |
| ????35 | ????4.352 | ????439.32 | ????86.66357 | |
| ????40 | ????4.1565 | ????444.68 | ????87.23876 | |
| ????45 | ????3.7825 | ????447.14 | ????88.34516 | |
| ????50 | ????3.5955 | ????449.76 | ????88.90135 | |
| Isothermal process | ????10 | ????19.1425 | ????285.0 | ????48.62125 |
| ????15 | ????15.808 | ????285.2 | ????56.34943 | |
| ????20 | ????12.376 | ????285.4 | ????64.78252 | |
| ????25 | ????11.3295 | ????286.0 | ????67.45741 | |
| ????30 | ????8.957 | ????285.8 | ????73.71191 | |
| ????35 | ????6.435 | ????285.4 | ????80.66627 | |
| ????40 | ????4.407 | ????285.1 | ????86.50214 | |
| ????45 | ????2.964 | ????285.0 | ????90.79456 | |
| ????50 | ????2.171 | ????284.8 | ????93.20509 |
Embodiment 6
Conversion condition: reaction pressure 8.25MPa, total dry gas volumetric flow rate: 65000m
3/ hour, water/dry gas 1.3, inlet gas is formed (butt): CO46%, CO
20.1%, H
2S3000ppm, CH
40.4%, surplus is H
2Catalyst loading in this example is in the tower tank reactor, and the inlet transformation temperature is 285 ℃.Reaction result is listed in table 6.
Table 6 catalyst loading is in the isothermal transform effect of tower tank reactor
| The catalyzer loading amount, m 3 | The CO outlet, % | Temperature out, ℃ | The CO transformation efficiency, % | |
| Isothermal process | ????10 | ????16.79 | ????286.0 | ????57.07 |
| ????20 | ????10.85 | ????285.2 | ????72.35 | |
| ????30 | ????7.85 | ????285.4 | ????80.71 | |
| ????40 | ????3.86 | ????286.0 | ????92.59 | |
| ????50 | ????1.91 | ????285.8 | ????98.76 |
Claims (6)
1. carbon monoxide and steam reaction are produced the isothermal sulfur-tolerant conversion process of hydrogen and carbonic acid gas, comprising:
(1) catalyst loading is in the tube bank of shell and tube reactor or in the tower still formula isothermal sulfur-tolerant conversion reactor of built-in coil pipe;
(2) unstripped gas at first through the gas heater heating, enters the isothermal sulfur-tolerant conversion reactor then, and the process gas of leaving reactor enters into purification section through after the heat exchange;
(3) a large amount of steam that produce in the reaction process enter to be located at and obtain circulation or recovery in the outer water-steam drum of reactor.
2. technology as claimed in claim 1, when it is characterized in that catalyst loading is in the tower tank reactor, corresponding heat-transfer medium cycling element and the heat exchange unit of changing into of described drum.
3. technology as claimed in claim 1 is characterized in that described reactor operating pressure between 1～10.0Mpa, and temperature of reaction is between 180～450 ℃.
4. technology as claimed in claim 1 is characterized in that described isothermal sulfur-tolerant conversion reactor can be one section, also can increase to two sections or three sections according to actual needs.
5. technology as claimed in claim 1 is characterized in that in the described unstripped gas that CO contents on dry basis scope is 1～75%.
6. technology as claimed in claim 1 is characterized in that described unstripped gas comprises: the synthetic gas that coal water slurry gasification technology produces, the synthetic gas that the coal gasification method produces, the synthetic gas that the residual oil partial oxidation process produces.
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|---|---|---|---|
| CN 01142861 CN1204038C (en) | 2001-12-30 | 2001-12-30 | CO isothermal sulfur resistant conversion process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01142861 CN1204038C (en) | 2001-12-30 | 2001-12-30 | CO isothermal sulfur resistant conversion process |
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|---|---|
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| CN1204038C CN1204038C (en) | 2005-06-01 |
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|---|---|---|---|
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100336715C (en) * | 2005-06-07 | 2007-09-12 | 昆明理工大学 | Process for preparing hydrogen by part changing of yellow phosphorus tail gas |
| CN101157442B (en) * | 2007-04-27 | 2010-07-21 | 中国石化集团宁波工程有限公司 | Waste heat reclaiming process for CO transformation |
| CN101955154A (en) * | 2010-10-25 | 2011-01-26 | 付元波 | Isothermal conversion process method for high-concentration carbon monoxide conversion |
| CN102001623A (en) * | 2010-11-01 | 2011-04-06 | 中国五环工程有限公司 | Process method for converting entrained-bed coal gasification high-concentration carbon monoxide |
| CN101050390B (en) * | 2007-04-27 | 2011-04-27 | 中国石化集团宁波工程有限公司 | CO conversion technique matched to coal gasification |
| CN101704513B (en) * | 2009-08-13 | 2011-11-16 | 上海国际化建工程咨询公司 | Shunting-type isothermal sulfur-tolerant conversion process and equipment thereof |
| CN102976270A (en) * | 2012-09-18 | 2013-03-20 | 东华工程科技股份有限公司 | Novel CO isothermal conversion method |
| CN103449365A (en) * | 2013-04-28 | 2013-12-18 | 山东齐鲁科力化工研究院有限公司 | High-concentration CO sulfur tolerant shift process and device thereof |
| CN103508416A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | CO (Carbonic Oxide) sulfur-tolerant shift catalytic reaction process |
| CN103641067A (en) * | 2013-12-05 | 2014-03-19 | 天脊煤化工集团股份有限公司 | Carbon monoxide isothermal-transformation process method |
| CN103881765A (en) * | 2014-03-24 | 2014-06-25 | 中石化宁波工程有限公司 | Split circulating CO transformation process |
| CN105561889A (en) * | 2014-10-23 | 2016-05-11 | 新煤化工设计院（上海）有限公司 | Radial flow by-product steam isothermal shift converter |
| CN112142003A (en) * | 2019-06-27 | 2020-12-29 | 中石化南京化工研究院有限公司 | Carbon monoxide conversion process |
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2001
- 2001-12-30 CN CN 01142861 patent/CN1204038C/en not_active Expired - Lifetime
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100336715C (en) * | 2005-06-07 | 2007-09-12 | 昆明理工大学 | Process for preparing hydrogen by part changing of yellow phosphorus tail gas |
| CN101157442B (en) * | 2007-04-27 | 2010-07-21 | 中国石化集团宁波工程有限公司 | Waste heat reclaiming process for CO transformation |
| CN101050390B (en) * | 2007-04-27 | 2011-04-27 | 中国石化集团宁波工程有限公司 | CO conversion technique matched to coal gasification |
| CN101704513B (en) * | 2009-08-13 | 2011-11-16 | 上海国际化建工程咨询公司 | Shunting-type isothermal sulfur-tolerant conversion process and equipment thereof |
| CN101955154A (en) * | 2010-10-25 | 2011-01-26 | 付元波 | Isothermal conversion process method for high-concentration carbon monoxide conversion |
| CN102001623B (en) * | 2010-11-01 | 2012-08-29 | 中国五环工程有限公司 | Process method for converting entrained-bed coal gasification high-concentration carbon monoxide |
| CN102001623A (en) * | 2010-11-01 | 2011-04-06 | 中国五环工程有限公司 | Process method for converting entrained-bed coal gasification high-concentration carbon monoxide |
| CN103508416A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | CO (Carbonic Oxide) sulfur-tolerant shift catalytic reaction process |
| CN102976270A (en) * | 2012-09-18 | 2013-03-20 | 东华工程科技股份有限公司 | Novel CO isothermal conversion method |
| CN103449365A (en) * | 2013-04-28 | 2013-12-18 | 山东齐鲁科力化工研究院有限公司 | High-concentration CO sulfur tolerant shift process and device thereof |
| CN103641067A (en) * | 2013-12-05 | 2014-03-19 | 天脊煤化工集团股份有限公司 | Carbon monoxide isothermal-transformation process method |
| CN103881765A (en) * | 2014-03-24 | 2014-06-25 | 中石化宁波工程有限公司 | Split circulating CO transformation process |
| CN105561889A (en) * | 2014-10-23 | 2016-05-11 | 新煤化工设计院（上海）有限公司 | Radial flow by-product steam isothermal shift converter |
| CN112142003A (en) * | 2019-06-27 | 2020-12-29 | 中石化南京化工研究院有限公司 | Carbon monoxide conversion process |
| CN112142003B (en) * | 2019-06-27 | 2022-05-17 | 中石化南京化工研究院有限公司 | Carbon monoxide conversion process |
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Owner name: CHINA PETROLEUM & CHEMICAL CORPORATION Free format text: FORMER OWNER: QILU PETROCHEMICAL GROUP CO., CHINA PETROCHEMICAL CORP. Effective date: 20071228 |
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Effective date of registration: 20071228 Address after: Zibo Linzi Shandong District Sinopec Qilu Branch science and Technology Department Patentee after: Sinopec Corp. Address before: 124 mailbox, Zibo City, Shandong Province Patentee before: Qilu Petrochemical Co., China Petrochemical Group Corp. |
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Granted publication date: 20050601 |