CN1197938C - Method of providing hydrogen for reforming under-stream - Google Patents
Method of providing hydrogen for reforming under-stream Download PDFInfo
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- CN1197938C CN1197938C CN 02109678 CN02109678A CN1197938C CN 1197938 C CN1197938 C CN 1197938C CN 02109678 CN02109678 CN 02109678 CN 02109678 A CN02109678 A CN 02109678A CN 1197938 C CN1197938 C CN 1197938C
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Abstract
The present invention belongs to a starting technique for a reforming device, particularly to a method for using crude gasoline as a raw material to prepare reformed-starting hydrogen gas. In the method, hydrogen gas generated by crude gasoline through a hydrogen preparing reactor is used for the gas-phase vulcanization of a hydrogenation refining catalyst; simultaneously, H2S components in the hydrogen gas are eliminated; next, the hydrogen gas is directly used for the starting operation of a double (multiple) metal reforming catalyst after being dried by a drying pot. When the hydrogen gas used for the starting operation of the catalytic reforming device is prepared by the method, a desulfurizing agent is not needed, sulphur in crude gasoline as the raw material can be used, and the activity and the stability of the hydrogenation refining catalyst are simultaneously enhanced. The method can directly use the crude gasoline whose the sulfur content is not greater than 800 mug/g and the arsenic content is not greater than 1500PPb to prepare qualified hydrogen gas.
Description
1, technical field
The present invention relates to a kind of reformer start-up method, specifically a kind of is the method that raw material is produced reforming under-stream hydrogen with the raw gasline.
2, technical background
It is to buy pure hydrogen that the going into operation of reformer needs purified hydrogen, traditional method, but cost height, very flexible.Patent 91100635 has been introduced the method that a kind of catalytic reforming unit goes into operation, and adopts sulphur content to be not more than hydrogen or treated oil that raw gasline that 300 μ g/g, arsenic content are not more than 1500PPb directly goes into operation and provides qualified for two (many) metal reforming catalysts.In this patent, providing a kind of is the technology of raw material reforming under-stream hydrogen with the raw gasline: raw gasline enters hydrogen-manufacturing reactor and produces hydrogen behind interchanger, process furnace, reaction product enters gas-liquid separator again behind interchanger and water cooler, product liquid returns material tank, a gas part is used as the hydrofining systemic circulation, and another part drying jar and digester are handled the back for the reforming system use that goes into operation.The shortcoming of this method is to adopt the sweetening agent be seated in the digester to remove H in the hydrogen
2S gas.In above-mentioned technological process, raw gasline produces H through behind the hydrogen-manufacturing reactor
2S contains H from the hydrogen that gas-liquid separator separates goes out
2S gas, these H
2S gas all needs to remove by sweetening agent.Sweetening agent removes H
2The ability of S is limited, and can not regenerate, and can only disposablely use, and the price of sweetening agent is also relatively more expensive.If sulphur content is higher in the raw gasline, the H in the hydrogen
2S content is also high, and perhaps the catalytic reforming unit required amounts of hydrogen that goes into operation is more, is the quality that guarantees hydrogen, must prepare sweetening agents more, fills in to switch in several digesters and uses, and this has just increased the cost that goes into operation, and obviously is unfavorable for increasing economic efficiency." refining of petroleum and chemical industry " the 29th volume the 5th phase P4～P7 is on the basis of this patent, change the order that goes into operation, earlier with hydrogen-manufacturing reactor and hydrofining reactor series connection, produce treated oil, then this treated oil is obtained more purified hydrogen by hydrogen-manufacturing reactor separately, its subject matter is that treated oil is by the product of hydrogen-manufacturing reactor, passes through hydrogen-manufacturing reactor once more, it is lower to produce the hydrogen rate, needs the time longer.
3, summary of the invention
The objective of the invention is to overcome the defective that prior art exists, provide a kind of economical and practical be the method that raw material is produced reforming under-stream hydrogen with the raw gasline, can directly use sulphur content to be not more than raw gasline that 800 μ g/g, arsenic content are not more than 1500PPb and produce the go into operation qualified hydrogen of usefulness of two (many) metal reforming catalysts.
Technical solution of the present invention is as follows: raw gasline is passed through hydrogen-manufacturing reactor, reaction product is cooled off, gas-liquid separation, gas phase is passed through hydrofining reactor after heating, the metal oxide generation vulcanization reaction in hydrogen sulfide and the Hydrobon catalyst wherein, simultaneously Hydrobon catalyst partly changes active higher sulphided state into from oxidation state, comes out behind the qualified hydrogen desiccation of hydrogen sulfide content as the go into operation hydrogen of usefulness of reformer from hydrofining reactor.For keeping the hydrogen generating system normal running, hydrogen can partly loop back the feedstock pump exit, and when hydrogen sulfide content was defective in the hydrogen, hydrogen all circulated.The process that the oxidation state Hydrobon catalyst absorbs hydrogen sulfide in the hydrogen promptly is the sulfidation of catalyzer.
The present invention compared with prior art has the following advantages:
(1) changed in the prior art and removed H by inorganic reaction
2The mode of S adopts Hydrobon catalyst gas phase sulfurized method, has guaranteed the H in the hydrogen
2S content meets the requirement that two (many) metal reforming catalysts go into operation.
(2) need not prepare expensive sweetening agent, and make the H in the hydrogen
2S gas has obtained sufficient recycling, has improved the economic benefit of refinery.
(3) in the operation process afterwards, Hydrobon catalyst has been in the partial vulcanization state, and is highly beneficial to the activity and the stability of performance Hydrobon catalyst.
(4) the present invention is specially adapted to use the raw gasline of sulphur content higher (being not more than 800 μ g/g) to carry out going into operation of catalytic reforming unit, can directly produce the go into operation qualified hydrogen of usefulness of two (many) metal reforming catalysts.
4, description of drawings
Fig. 1 is a process flow diagram of the present invention.
Wherein 1 is the hydrofining fresh feed pump, the 2nd, and process furnace, the 3rd, hydrogen-manufacturing reactor, the 4th, hydrofining reactor, the 5th, air cooling, the 6th, water-cooled, the 7th, gas-liquid separator, the 8th, compressor, the 9th, process furnace, the 10th, drying chamber.Further specify process of the present invention and effect below in conjunction with accompanying drawing.
5, embodiment
The inventive method specific operation process is: with raw gasline process hydrofining fresh feed pump 1, again through entering hydrogen-manufacturing reactor 3 after process furnace 2 heating, after the sorbent treatment through the filling of hydrogen-manufacturing reactor upper strata, at 400～460 ℃ of hydrogen-manufacturing reactor temperature ins, pressure 0.3～0.7MPa, volume space velocity 4～40h
-1, gas and oil volume ratio 100～500: 1 processing condition under, carry out the naphthenic hydrocarbon dehydrogenation reaction and produce hydrogen, reaction product enters gas-liquid separator 7 after 6 coolings of air cooling 5, water-cooled.The product liquid that obtains from gas-liquid separator 7 returns material tank, the hydrogen that obtains from gas-liquid separator 7 passes through compressor 8, again through entering hydrofining reactor 4 behind the process furnace 9, the gas that comes out from hydrofining reactor 4 returns 1 outlet of hydrofining fresh feed pump and recycles for pre-hydrogenation system.After pre-hydrogenation system pressure rises to the required pressure of Hydrobon catalyst sulfuration, process furnace 9 igniting, hydrofining reactor 4 temperature ins rise to 150～200 ℃ of constant temperature with the speed of 15～30 ℃/h, are preferably 175 ℃, begin to carry out the gas phase sulfuration of Hydrobon catalyst.After the hydrogen that comes out from hydrofining reactor 4 was qualified, a part recycled for pre-hydrogenation system, another part through drying chamber 10 dryings after, for the use that goes into operation of two (many) metal reforming catalysts.
H in the timing analysis reformation reduction hydrogen
2S content.Work as H
2When S content is defective, hydrogen is all used as recycle hydrogen, simultaneously hydrofining reactor 4 temperature ins are risen to 200～240 ℃ with the speed of 15～20 ℃/h and continue the constant temperature sulfuration, be preferably 230 ℃, the H in the hydrogen
2When S content is qualified, continues as two (many) metal reforming catalysts and go into operation qualified hydrogen is provided.After this sulfuration finishes, repeat above-mentioned steps in stage, the hydrofining reactor temperature in is risen to 280～320 ℃ with the speed of 15～20 ℃/h continue the constant temperature sulfuration, be preferably 290 ℃, finish until sulfuration.In said process, if enough being used for two (many) metal reforming catalysts, hydrogen goes into operation, can finish the gas phase sulfuration of Hydrobon catalyst in advance, carry out going into operation of catalytic reforming unit by normal step.
In above-mentioned hydrogen-manufacturing reactor, the upper strata filled with adsorbent is to remove impurity such as arsenic in the raw gasline, sulphur; Lower floor's filling catalyst for preparing hydrogen, purpose is to be that raw material is produced hydrogen with the raw gasline.Sorbent material is 0.5～3: 1 (weight) with the filling ratio of catalyzer.Above-mentioned sorbent material is the mixture of dearsenic agent and sweetening agent, and the filling ratio of two kinds of sorbent materials is 0.5～4: 1 (weight).Above-mentioned catalyst for preparing hydrogen is single platinum catalyst, and platinum content is 0.3～0.6% (weight).
In above-mentioned hydrofining reactor, the filling Hydrobon catalyst, purpose has two, and the one, in the process of producing reforming under-stream hydrogen, the H in the absorption hydrogen
2S gas carries out the gas phase sulfuration of catalyzer; The 2nd, in normal productive process, raw gasline is carried out hydrofining, make treated oil meet the catalytic reforming feedstock requirement.Above-mentioned Hydrobon catalyst is that the oxide compound with VI family and VIII metal supports on refractory inorganic oxide carrier material of either and makes normal carrier that uses such as aluminum oxide, silicon oxide, siliceous aluminum oxide etc.
The hydrogen that obtains from gas-liquid separator need be through the process furnace heating, reach specified temperature after, enter hydrofining reactor, carry out the gas phase sulfuration of Hydrobon catalyst.
Before hydrogen is used for catalytic reforming unit and goes into operation, need to have the material of water sorption such as the drying chamber of molecular sieve is handled to remove moisture through filling.
Adopt method provided by the invention, can directly use sulphur content to be not more than raw gasline that 800 μ g/g, arsenic content are not more than 1500PPb and produce the go into operation qualified hydrogen of usefulness of two (many) metal reforming catalysts.
Further introduce technical characterstic of the present invention below by example.
Embodiment
Raw material: straight-run spirit, sulphur content 300 μ g/g, arsenic content 10PPb.
Hydrogen-manufacturing reactor upper strata filling RAS-1 sorbent material (Chang Ling refinery product) and T-302 sorbent material (Nanjing Chemical Industry Company's product), the filling ratio of two kinds of sorbent materials is 1: 2 (weight); 3944 catalyzer (Fushun Petrochemical Company catalyst plant product) load in lower floor, and sorbent material is 2: 1 (weight) with the filling ratio of catalyzer.Filling 481-3 catalyzer (Wenzhou Hua Hua group company product) in the hydrofining reactor.
The hydrofining system feeds nitrogen and boosts to 0.5MPa, and hydrogen-manufacturing reactor is warming up to 400 ℃, raw gasline is introduced hydrogen-manufacturing reactor produce hydrogen, and reaction product enters gas-liquid separator after air cooling, water-cooled cooling.The product liquid that obtains from gas-liquid separator returns material tank, and the hydrogen process compressor from gas-liquid separator obtains enters hydrofining reactor through behind the process furnace again, and the gas that comes out from hydrofining reactor all uses as recycle hydrogen.After pre-hydrogenation system pressure rises to 1.5MPa, the process furnace igniting, the hydrofining reactor temperature in rises to 175 ℃ of constant temperature with the speed of 20 ℃/h, begins to carry out the gas phase sulfuration of Hydrobon catalyst.From the qualified back of hydrogen (hydrogen sulfide content 0.2PPm) that hydrofining reactor comes out, except that the pre-hydrogenation system of a small amount of confession recycles, remaining hydrogen is through (water-content 10PPm) bottling storage after molecular sieve drying, for the use that goes into operation of pair (many) metal reforming catalysts.When outlet hydrogen sulfide content when defective, rise to 230 ℃ with the speed of 20 ℃/h, underproof hydrogen all circulates in this process.Through temperature raising, after hydrogen is qualified, again hydrogen is used for reformer after drying and goes into operation.When hydrogen satisfy reformer go into operation use after, stop said process.
Claims (8)
1, a kind of is raw material with the raw gasline, producing reformer goes into operation with the method for hydrogen, raw gasline is passed through hydrogen-manufacturing reactor, reaction product is cooled off, gas-liquid separation, it is characterized in that the gas phase process after the gas-liquid separation heats the back by being filled with the reactor of Hydrobon catalyst, hydrogen sulfide is absorbed by the metal oxide in the Hydrobon catalyst, Hydrobon catalyst changes sulphided state into from oxidation state, the hydrogen that the hydrogen sulfide content that comes out from hydrofining reactor is qualified goes into operation as reformer after drying and uses hydrogen, wherein the operational condition of hydrogen sulfide is in the oxidation state Hydrobon catalyst absorption hydrogen: at 150～200 ℃ of following constant temperature absorbing hydrogen sulphides of reactor inlet temperature, be warming up to 200～240 ℃ of constant temperature absorbing hydrogen sulphides after outlet hydrogen sulfide is defective, outlet hydrogen sulfide is warming up to 280～320 ℃ of constant temperature absorbing hydrogen sulphides after defective, and sulfidation terminates in qualified amounts of hydrogen satisfies the demand.
2, in accordance with the method for claim 1, it is characterized in that describedly when hydrogen sulfide content is defective from the hydrogen that hydrofining reactor comes out, hydrogen all loops back the feedstock pump outlet.
3, in accordance with the method for claim 1, it is characterized in that described Hydrobon catalyst is that oxide compound by VI family and VIII metal supports on refractory inorganic oxide carrier material of either and makes.
4, in accordance with the method for claim 1, it is characterized in that described hydrogen-manufacturing reactor filled with adsorbent at the middle and upper levels, lower floor's filling catalyst for preparing hydrogen.
5, in accordance with the method for claim 4, it is characterized in that described sorbent material comprises desulfuration adsorbent and dearsenification sorbent material, two kinds of sorbent material mixed packings, its weight ratio is 0.5～4: 1.
6, in accordance with the method for claim 4, it is characterized in that the described sorbent material and the charge weitght ratio of catalyst for preparing hydrogen are 0.5～3: 1, catalyst for preparing hydrogen is that the platinum weight content is single platinum catalyst of 0.3～0.6%.
7, in accordance with the method for claim 1, it is characterized in that described hydrogen-manufacturing reactor operational condition is: 400～460 ℃ of temperature ins, pressure 0.3～0.7MPa, volume space velocity 4～40h
-1, gas and oil volume ratio 100～500: 1.
8, in accordance with the method for claim 1, it is characterized in that described hydrogen desiccation adopts the molecular sieve adsorption method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02109678 CN1197938C (en) | 2002-05-15 | 2002-05-15 | Method of providing hydrogen for reforming under-stream |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02109678 CN1197938C (en) | 2002-05-15 | 2002-05-15 | Method of providing hydrogen for reforming under-stream |
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| CN1458231A CN1458231A (en) | 2003-11-26 |
| CN1197938C true CN1197938C (en) | 2005-04-20 |
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| CN 02109678 Expired - Lifetime CN1197938C (en) | 2002-05-15 | 2002-05-15 | Method of providing hydrogen for reforming under-stream |
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| CN104611061B (en) * | 2013-11-05 | 2016-08-17 | 中国石油化工股份有限公司 | The method that a kind of reformed pre-hydrogenated and catalytic reforming process goes into operation simultaneously |
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