WO2010045769A1

WO2010045769A1 - Method and device for short-flow desulfurizing recyled hydrogen

Info

Publication number: WO2010045769A1
Application number: PCT/CN2008/073594
Authority: WO
Inventors: 汪华林; 马吉; 钱卓群; 张艳红; 李立权; 曾茜; 陈崇刚; 杨强; 徐效梅; 崔馨
Original assignee: 上海华畅环保设备发展有限公司; 中国石化集团洛阳石油化工工程公司
Priority date: 2008-10-24
Filing date: 2008-12-19
Publication date: 2010-04-29
Also published as: RU2430012C1; CN101434381B; CN101434381A

Abstract

A method for short-flow desulfurizing recycled hydrogen, involves the following steps: (a) subjecting recycled hydrogen mixed gas to remove hydrocarbon (10), in order to separate disperse phase heavy hydrocarbon liquid drops from continuous phase recycled hydrogen, and obtain heavy hydrocarbon phase and sulfur-containing mixed phase; (b) further separating the mixed phase to remove sulfide and obtaining sulfur-free recycled hydrogen; (c) further separating sulfur-free recycled hydrogen to remove amine liquid (9) and obtaining purified recycled hydrogen (6). A device for short-flow desulfurizing recycled hydrogen is also provided.

Description

Short process cyclic hydrogen desulfurization method and device

The invention relates to the field of waste gas treatment, and relates to a method for removing sulfide in a circulating hydrogen mixture, in particular, the invention relates to a short-flow purification treatment method for sulfur-containing circulating hydrogen in a hydrogenation process, and The device used in the method. Background technique

In recent years, the number of China's imports of sour crude oil increased year by year, in 2002 crude oil imports reached 6.9 X 10 ⁷ tons. As the crude oil in the Middle East-Arab countries is high-sulfur crude oil, the proportion of imported sulfur-containing crude oil in processing crude oil has increased year by year. The sulfur content in the circulating hydrogen during the hydrogenation process increases with the increase of the sulfur content of the crude oil, increases the molecular weight of the recycled hydrogen, increases the energy consumption of the circulating hydrogen compressor, reduces the purity of the hydrogen, and shortens the service life of the catalyst. Reaction efficiency.

The current common problems in hydrogenation units are: circulating hydrogen, liquid hydrocarbons, diesel, sulfur-containing sewage and low-gas separation entraining dispersed phase particles of heavy hydrocarbons, amines, water, catalysts, etc., which not only increases the consumption of additives and raw materials. Loss, and it brings great harm to the long-term operation of downstream key equipment. Circulating hydrogen, liquid hydrocarbons and low-gas entrainment of heavy hydrocarbons will cause circulating hydrogen, liquid hydrocarbons and low-gas desulfurization tower solvents to foam, causing the amine to run off. For the amount of amine run loss, the difference between the production facilities is as low as 0.05 kg / ton dry gas, 0.1 kg / ton of liquefied petroleum gas, up to 1.0 kg / ton dry gas, 10 kg / ton of liquefied petroleum gas. The loss of the amine fluid will cause secondary pollution to the sewage system, which directly burdens the sewage treatment plant; in addition, the circulating hydrogen-containing liquid and dusting pose a serious threat to the long-term operation of the compressor. At present, all refineries have varying degrees of circulating hydrogen, liquid hydrocarbons, diesel, sulphur-containing sewage, low-gas separation, and dust-carrying problems. These problems can be attributed to the category of heterogeneous separation, design and production operations. An urgent problem to be solved.

Solve the problem of circulating hydrogen, liquid hydrocarbons, diesel oil, sulfur-containing sewage and low-gas distribution with liquid and dust. The previous process was to use a coalescer to remove it. However, the long-term operation time guaranteed by the domestic and foreign supplier technical agreements of the coalescer is only one year, which cannot meet the requirements of the three-year maintenance guided by Sinopec. If the operating cycle is guaranteed to be three years, the diameter of the coalescer must be increased to the diameter of the reactor, the cost is high, and the floor space is large; and the coalescer must be equipped with a bypass system, which does not meet the general design of the high pressure system. specification. According to the survey, the heavy hydrocarbon coalescing device of the circulating hydrogen of Sinopec Maoming Branch can only run for one year and cannot meet the long-term operation requirements of three years.

Regarding the problem of circulating hydrogen, liquid hydrocarbons and low-gas entrained amine liquid at the outlet of the desulfurization tower, the design usually adopts sedimentation. The tank is deliquored and dusted. However, amine desulfurization has a "solvent foaming" problem that has not been completely solved so far, that is, rapid loss of amine liquid. The amine liquid itself has a tendency to foam. When the content of heavy hydrocarbons such as C5 in the system is large, system impurities such as HSS content is high, and even iron embroidery is more (such as the system alkali washing pretreatment is not perfect before the start of the new plant), foaming will occur. Under the induction of the foaming agent, once the amine solution is foamed, it will develop in the direction of growth. The defoaming agent can temporarily control the foaming tendency, but once it exceeds a certain limit, it will develop into an insurmountable foaming plug. Causes the compressor to operate abnormally.

Therefore, the efficient, safe, environmentally coordinated and long-term operation of the hydrocracking unit's circulating hydrogen, liquid hydrocarbon, diesel, sulfur-containing wastewater and low-gas separation heterogeneous particle separation systems is undoubtedly the future development direction.

Units such as the School of Mechanical and Materials Engineering of Washington State University have designed miniature cyclones of 5mm, 10mm, 15mm, and 25mm. With the 19mm cyclone separator, the separation efficiency of the aerosol particles of 3μηι biomass can reach 95%, and the separation efficiency of the aerosol particles of 2μηι biomass can reach more than 80%. However, research is still in the laboratory stage, and industrial applications still need to solve many problems.

China has also done a lot of work in the industrial application of cyclone separation. Chinese patent CN 200995173Y invented a gas-liquid cyclone separator, CN 2912804 Υ discloses a multi-column cone combined liquid-liquid separation cyclone, The cyclone body is composed of a plurality of column segments, a tapered segment alternately connected and a tail pipe. Innovations in the structure of cyclone separation equipment are continually expanding the field of application of cyclonic separation, but the use of cyclonic separation methods with low density differences and high separation accuracy is still technically limited.

In short, due to the above problems existing in the prior art, the scientific purification treatment problem of the sulfur-containing circulating hydrogen mixture gas has not been solved so far, which is far from meeting the expectation of petrochemical clean production industrialization. Therefore, there is an urgent need in the art to develop a treatment method and apparatus for a sulfur-containing circulating hydrogen mixture which is low in cost and effective in effect. Summary of the invention

The present invention provides a new short process cyclic hydrogen desulfurization method and apparatus that overcomes the deficiencies of the prior art.

In one aspect, the invention provides a short process cyclic hydrogen desulfurization process, the method comprising the steps of:

(a) dehydrogenating the recycled hydrogen mixture gas to separate the dispersed phase heavy hydrocarbon droplets from the continuous phase circulating hydrogen to obtain a mixed phase of the heavy hydrocarbon phase and the sulfur-containing circulating hydrogen;

(b) further separating the resulting mixed phase to remove the sulfide therein to obtain a sulfur-free circulating hydrogen; (C) further separating the obtained sulfur-free circulating hydrogen to remove the amine liquid therein to obtain purified circulating hydrogen.

In a preferred embodiment, after the mixed phase obtained in the step (a) is desulfurized by the step (b), the concentration of the sulfide is reduced to 10 ppm or less.

In another preferred embodiment, when the mixed phase of the step (a) has an amine liquid content of not more than

4000mg / Nm ³ when over said step (c) after removal of the amine content of the resulting free amine hydrogen purge cycle is not greater than 20mg / Nm ^3.

In another aspect, the present invention provides a short process cyclic hydrogen desulfurization apparatus, the apparatus comprising:

Used for dehydrogenating a circulating hydrogen mixture gas to separate dispersed heavy hydrocarbon droplets from continuous phase circulating hydrogen to obtain a dehydrogenator of a heavy hydrocarbon phase and a mixed phase of sulfur-containing circulating hydrogen; Connected to the gas phase outlet of the vessel for further separating the resulting mixed phase to remove sulfide therein to obtain a sulfur-free circulating hydrogen desulfurization tower; and in the desulfurization tower for further separation Sulfur-free circulating hydrogen to remove the amine liquid therefrom to obtain a purified recycle hydrogen deaminator.

In a preferred embodiment, the deaminator is selected from the group consisting of a gravity settling tank, a coalescer, and a hydrocyclone.

In another preferred embodiment, the deaminator recovers from the amine liquid by a particle size of up to 5 microns, a recovery of more than 90% for droplets greater than 10 microns, and a separation time of from 1 to 3 seconds.

In another preferred embodiment, when the hydrocarbon component in the dehydrogenator is C5 or higher, the calculated separation precision of the droplet is 3 micrometers, and the removal rate of droplets above 5 micrometers exceeds 95. %; The droplet separation precision of liquid hydrocarbon, diesel, and sulfur-containing sewage is 15 μm, and the removal rate of droplets of 25 μm or more exceeds 95%; the pressure drop of the dehydrogenator is less than 0.15 MPa.

In another preferred embodiment, when the heavy hydrocarbon content of the inlet of the dehydrogenator is not more than 1350 mg/m ³ , the outlet heavy hydrocarbon content of the bottom outlet is a trace amount.

In another preferred embodiment, the apparatus further includes a screen eliminator added in front of the deaminator for initially removing the mixture entering the cyclone separator built into the top of the desulfurization tower. Part of the droplets and solid particles.

In another preferred embodiment, the rich amine solution of the desulfurization tower is discharged from the bottom effusion chamber into the amine liquid regeneration tower, and the lean amine from the regeneration tower is mixed into the supplementary amine liquid and is sent to the desulfurization tower for recycling. The amine consumption is reduced by 60%. DRAWINGS

1 is a schematic diagram of a short process cyclic hydrogen desulfurization process in accordance with an embodiment of the present invention.

Figure 2 is a schematic illustration of a hydrocracking cycle hydrogen desulfurization process incorporating the short process recycle hydrogen desulfurization process of the present invention. detailed description

After extensive and intensive research, the inventors of the present invention found that for the cyclic hydrogen desulfurization treatment, an effective combination of a dehydrogenation unit, a desulfurization tower and a deaminator placed in the desulfurization tower can obtain a low investment cost of the equipment, occupying land. The utility model has the advantages of small area, low failure rate, good treatment effect of circulating hydrogen mixed gas, and can effectively solve the problems of running off of amine liquid, solvent foaming, etc., improving the service life and reaction efficiency of the catalyst, and reducing the energy consumption of the short-flow circulating hydrogen desulfurization device. Based on the above findings, the present invention has been completed.

In the present invention, the desulfurization tower circulating hydrogen inlet settling tank is miniaturized, the gravity sedimentation tank of the desulfurization tower circulating hydrogen outlet is eliminated, and the low pressure separation tank is built in a separator, instead of the circulating hydrogen desulfurization tower inlet circulating hydrogen cyclone, A new ultra-short process cyclic hydrogen desulfurization process with no separation equipment before and after the inlet and outlet of the desulfurization tower is formed.

In a first aspect of the invention, there is provided a cyclic hydrogen desulfurization treatment method comprising the steps of:

(a) circulating hydrogen mixed gas through the dehydrogenator, separating the dispersed phase heavy hydrocarbon droplets from the continuous phase circulating hydrogen to obtain a mixed phase of the heavy hydrocarbon phase and the sulfur-containing circulating hydrogen;

(b) further separating the obtained recycled hydrogen mixture gas, removing the sulfide therein to obtain a sulfur-free circulating hydrogen;

(c) further separating the obtained gas phase, and removing the amine liquid therein to obtain purified circulating hydrogen.

Preferably, when the heavy hydrocarbon content of the inlet of the circulating hydrogen dehydrogenator is not more than 1350 mg/m ³ , the heavy hydrocarbon content of the bottom outlet is a trace amount.

Preferably, in the step (a), the hydrocarbon component in the circulating hydrogen dehydrogenator is C5 and above, the droplet separation precision is 3 micrometers, and the removal rate of droplets above 5 micrometers exceeds 95%; The droplet separation precision of liquid hydrocarbon, diesel and sulfur-containing sewage is 15 micrometers, and the removal rate of droplets above 25 micrometers exceeds 95%; the pressure drop is less than 0.015 MPa.

Preferably, after the recycled hydrogen mixture obtained in the step (a) is desulfurized by the desulfurization absorbent of the step (b), the sulfide concentration in the mixture may be lowered to 10 ppm or less.

Preferably, when the liquid content of the amine inlet gas mixture is not more than 4000mg Nm ³ hour / via step (c), the free amine content of the purified gas is not more than 20mg / Nm ^3.

Preferably, in step (c), the demineralizer recovers the amine liquid by a particle size of up to 5 micrometers, for more than 10 The recovery of micron droplets is greater than 90% and the separation time is 1-3 seconds. The content of the droplets at the overflow of the cyclone separator is not more than 20 mg/m ³ .

In a second aspect of the invention, there is provided an apparatus for use in the above method, comprising:

a dehydrogenator for separating heavy hydrocarbon droplets, a desulfurization tower for absorbing sulfides connected to a gas phase outlet of the dehydrogenator, and an amine liquid absorbent for separating hydrogen contained in the sulfur removal process Deaminator.

Preferably, the dehydrogenator may select one or more of a gravity settling tank, a coalescer or a hydrocyclone according to processing precision requirements.

Preferably, the dehydrogenator is connected to the desulfurization tower through its gas phase outlet, and the heavy hydrocarbons and sewage are discharged from the bottom outlet of the dehydrogenator.

Preferably, an amine liquid separation device is added to the desulfurization tower, and the device may be any one of a gravity settling tank, a coalescer or a hydrocyclone. The device initially removes some droplets and solid particles in the mixture entering the top deaerator of the column to improve the separation efficiency of the gas-liquid two phases and prolong the cycle of the gas-liquid cyclone separator.

Preferably, the cyclic hydrogen desulfurization system of the present invention controls the foaming of the amine liquid well, avoiding a large amount of amine fluid run-off and reducing the amine consumption by 60%.

Preferably, the cyclic hydrogen desulfurization system of the present invention reduces the molecular weight of the recycled hydrogen by removing heavy hydrocarbons and water in the recycled hydrogen, and reduces the energy consumption of the compressor by about 12%.

Preferably, the recycled hydrogen desulfurization system of the present invention increases the purity of the recycled hydrogen by 2.2%, which is equivalent to an increase of 2.2% in the partial pressure of hydrogen. According to the results of the SSOT of the Middle Distillate, the catalyst life can be increased by 8.6 %.

Preferably, a screen eliminator is added in front of the deaminator in the desulfurization tower to initially remove a part of the droplets and solid particles in the mixture gas entering the top of the top of the cyclone separator to improve the gas-liquid two-phase separation. Efficiency, extending the life cycle of the gas-liquid cyclone separator.

Preferably, the rich amine solution of the desulfurization tower is discharged from the bottom liquid reservoir into the amine liquid regeneration tower for regeneration; the lean amine from the regeneration tower is mixed into the supplementary amine liquid and is recycled into the desulfurization tower for recycling, and the sulfide is processed into the subsequent treatment. Device. See the attached drawings below.

1 is a schematic diagram of a short process cyclic hydrogen desulfurization process in accordance with an embodiment of the present invention. As shown in Fig. 1, a circulating hydrogen mixture gas containing circulating hydrogen, hydrogen sulfide and hydrocarbons is sent to the dehydrogenator 1 for dehydrogenation to separate the dispersed phase heavy hydrocarbon droplets from the continuous phase circulating hydrogen to obtain a heavy hydrocarbon phase. a mixed phase with sulfur-containing circulating hydrogen; the obtained mixed phase exits the gas phase outlet 3 of the dehydrogenator 1 and enters the desulfurization tower 2 of the deaminator 5 for further separation to remove the sulfide therein, thereby obtaining no Sulfur-containing circulating hydrogen; obtained heavy hydrocarbons and sewage from desulfurization The bottom flow port 4 of the column 2 is discharged; the obtained sulfur-free circulating hydrogen is further separated by the deaminator 5 to remove the amine liquid therein to obtain purified circulating hydrogen, which is discharged from the top of the desulfurization tower 2; The amine liquid and hydrogen sulfide are discharged from the bottom of the desulfurization tower 2 into an amine liquid regeneration tower (not shown), and the lean amine from the regeneration tower is mixed into the supplementary amine liquid and sent to the desulfurization tower 2 for recycling.

Figure 2 is a schematic illustration of a hydrocracking cycle hydrogen desulfurization process incorporating the short process recycle hydrogen desulfurization process of the present invention. As shown in FIG. 2, after the feedstock oil is heated by the heating furnace 11, the purification reaction is carried out from the upper port of the hydrogenation reactor 12 into the reactor, and the sulfur-containing high-temperature substance enters from the upper port of the heat exchanger 13, and enters the air cooler 14 after initial cooling. Further cooling, a circulating hydrogen mixture containing hydrogen sulfide and a heavy hydrocarbon component is separated by a high pressure separator 15, and an oil is produced, wherein the generated oil is discharged from the bottom of the high pressure separator 15 as a liquid phase, and the circulating hydrogen mixture is discharged by a high pressure. The upper end outlet of the separator 15 enters the dehydrogenator 1, and the heavy hydrocarbon component entrained in the hydrogen is dehydrogenated by the dehydrogenator 1, and the separated heavy hydrocarbon component is discharged as a liquid phase from the lower end outlet of the dehydrogenator 1, and the sulfur-containing cycle Hydrogen is taken from the upper end of the dehydrogenator 1 into the desulfurization tower 2, and the sulfide in the circulating hydrogen is removed by the amine liquid absorption machine, the lean liquid is discharged from the bottom of the desulfurization tower 2, and the rich amine liquid is demineralized into the deaminator; The circulating hydrogen is driven into the heat exchanger 13 by the circulating hydrogen compressor 16, and the gas entering therein is subjected to a temperature lowering treatment, wherein the feedstock oil and the new hydrogen can directly enter the heat exchanger 13 and are taken up by the hydrogenation reactor 12. Preheating heat, and then into the furnace 11. The main advantages of the method and apparatus of the present invention are:

The equipment of the invention has low investment cost, small occupied area, low failure rate, good treatment effect of circulating hydrogen mixed gas, can effectively solve the problems of running off of amine liquid, solvent foaming, etc., improve the service life and reaction efficiency of the catalyst, and simultaneously reduce Energy consumption. Example

The invention is further illustrated by the following specific examples. However, it is to be understood that the examples are not intended to limit the scope of the invention. The test methods for which specific conditions are not specified in the following examples are usually carried out according to conventional conditions or according to the conditions recommended by the manufacturer. All percentages and parts are by weight unless otherwise indicated. China Petroleum & Chemical Corporation Zhenhai Refining & Chemical Company Refining Five Parts 1.5 Million Tons / Year Hydrocracking Unit Circulation Hydrogen Desulfurization System:

1. Process: The specific process flow is shown in Figure 2.

(1) Key equipment:

The key equipment in the process is dehydrogenerator 1 and desulfurization tower 2, wherein the dehydrogenation unit has a diameter of 2400 mm, a height of 9995 mm, and a treatment capacity of 280,000 Nm ³ /h.

(2) Control:

The flow rate of the circulating hydrogen into the dehydrogenator was 282,000 Nm ³ /h, the operating pressure was 13.5 MPa (gauge pressure), and the operating temperature was 50 °C.

(3) Operation effect:

The dehydrogenation of the circulating hydrogen dehydrogenator is efficient and stable. Under the working condition, the average deliquoring is 1350mg/m ³ , and the content of C5 and above is reduced from the average of 38.42g/Nm ³ to 11.02 g/Nm ³ . The content decreased from an average of 6.5 g/Nm ³ to 1.6 g/Nm ³ . What is more remarkable is that the buffer tank after the circulating hydrogen desulfurization tower has not been liquid-deposited since it was put into use, indicating that the circulating hydrogen does not carry droplets after passing through the desulfurization tower, the desulfurization effect is good, the amine liquid does not foam, and the compressor is also No abnormalities occurred. According to the actual parameter analysis, the actual lean liquid volume of the desulfurization tower is about 35 tons / hour, and the design value is 55 tons / hour; the average content of H ₂ S in the recycled hydrogen is 1700ml / m ³ (up to 5000ml / m ³ , At a minimum of 200ml/m ³ ), H ₂ S is also well controlled under low lean liquid flow conditions.

2. Equipment operation calibration

See Table 1-2 below.

Table 1: Operation of low-dividing cyclone separator during calibration

Handling volume Operating pressure Imported liquid content Export liquid content Time Removal rate%

Nm ³ /h MPa mg/Nm ³ mg/Nm ³

March 25曰

3197 1.55 618 89 85.6 10: 00

March 26曰

3170 1.55 761 87 88.6 10: 00

March 27曰

3105 1.55 377 76 79.8 10: 00

March 31 曰

3438 1.55 792 123 84.5 10: 00

April 01 曰

4103 1.55 934 92 90.1 10: 00 From the above analysis data, the average deliquoring efficiency of the low-gas cyclone separator is 85.7%, and the outlet liquid is basically below 100mg/Nm ³ . Table 2: Operation of liquefied gas amine separator during calibration

From the above analysis data, it is known that the average separation efficiency of the liquefied gas amine separator is 73.0%, and the outlet liquid is below 100 ppm.

3. Operation effect (a) Amine consumption

Through the operation evaluation of the desulfurization system of the new device for a period of time, and comparing with the corresponding part of the old device (the old device is a 1 million tons/year hydrocracking device, and the sedimentation liquid separation tank is used before the circulating hydrogen desulfurization tower, the rest is the same) . The new unit consumes 30 tons of fresh amine solution a year, and the old unit consumes 55 tons, which is converted into a 1.5 million tons/year scale. The amine consumption is 83 tons per year, a 64% reduction.

(b) emission reduction effect

After the old unit desulfurization tower, the buffer tank has more liquid phase deposition, and the average liquid level is increased from 0 to 20% in 2-3 days, and the liquid is discharged once every two days. The discharged amine solution is calculated at a concentration of 25%, causing an accidental loss of 16 tons of fresh amine solution per year. The new device does not consume this part. Through analysis, the recirculating hydrogen cyclone dehydrogenator of the new device has better separation effect on the liquid carried by the circulating hydrogen, avoiding the foaming of the amine liquid caused by the high hydrogen content of the circulating hydrogen entrainment, thereby improving the efficiency of desulfurization and reducing The running loss of the amine solution.

(c) Long-term operation of the device

The circulating hydrogen desulfurization system not only consumes a small amount of amine liquid, but also operates smoothly and safely since the start of construction, and has never fluctuated. The circulating hydrogen desulfurization system must not only ensure the removal of H ₂ S, but also ensure the safe and stable operation of the circulating hydrogen compressor, which is also the key to the long-term stable operation of the plant. The entrainment of droplets in the gas can cause the compressor to slam, causing surge, and causing damage to the compressor, resulting in abnormal shutdown. Since the use of the circulating hydrogen cyclone dehydrogenator, the problem of circulating hydrogenated liquid has been fundamentally solved from the source, and the treatment mode of "first pollution, post-treatment" has been changed, and the long period of the device has been economically guaranteed. Safe and stable operation.

(d) Energy saving effect

Through the calibration result, the circulating hydrogen density of the inlet compressor is 181.4g/m ³ , and after separation by the cyclone dehydrogenator,

The content of C5 was lowered by 27.4 g/m ³ , and the content of H ₂ O was decreased by 4.9 g/m ³ , which was equivalent to a decrease in molecular weight of recycled hydrogen of 32.3 g/m ³ , which was reduced by 15.1%. With the compressor idle energy consumption accounting for 1/3 of the total energy consumption, the total energy consumption of the compressor is reduced by 10.1%.

(e) increase hydrogen purity

Due to the liquid separation of the circulating hydrogen cyclone dehydrogenator, the volume content of C5 in the circulating hydrogen is reduced from 1.00% to

0.33%, a decrease of 0.67%, and the volume content of H ₂ O decreased from 0.815% to 0.20%, decreased by 0.61%, and decreased by a total of 1.28%. This indirectly increases the concentration of circulating hydrogen. Calculated by the current hydrogen concentration of the compressor into 85.75%, the circulating hydrogen concentration before the reducing component liquid is 84.65%, which is equivalent to a 1.1% increase in concentration. This is advantageous in extending the life of the catalyst in the hydrogenation reactor and ensuring long-term operation.

Circulating hydrogen cyclone dehydrogenator in China Petroleum and Chemical Corporation Zhenhai Refining & Chemical Company 1.5 million tons / year Since it has been put into use in the desulfurization system of the hydrocracking unit, it has been running smoothly, easy to operate, easy to control, and meets the requirements of industrial production and environmental coordination. The high-efficiency separation technology of circulating hydrogen cyclone not only solves the problem of foaming of amine liquid caused by carrying high oil, but also reduces the running loss of amine liquid, and at the same time ensures the safe long-term operation of the compressor, with significant economic benefits and resources. benefit. All documents mentioned in the present application are hereby incorporated by reference in their entirety in their entireties in the the the the the the the the the In addition, it should be understood that various modifications and changes may be made by those skilled in the art after the above-described teachings of the present invention.

Claims

Rights request

A short process cyclic hydrogen desulfurization method, the method comprising the steps of:

(b) further separating the resulting mixed phase to remove the sulfide therein to obtain a sulfur-free circulating hydrogen;

(c) further separating the obtained sulfur-free circulating hydrogen to remove the amine liquid therefrom to obtain purified hydrogen.

The method according to claim 1, wherein the mixed phase obtained in the step (a) is desulfurized in step (b), and the concentration of the sulfide is reduced to 10 ppm or less.

The method according to claim 1 or 2, wherein, when the amine phase content of the mixed phase in the step (a) is not more than 4000 mg/Nm ³ , after the deamination after the step (c) The resulting purified amine has a free amine content of no more than 20 mg/Nm ³ .

4. A short process cyclic hydrogen desulfurization apparatus, the apparatus comprising:

It is used for dehydrocarbonating a circulating hydrogen mixture gas to separate the dispersed phase heavy hydrocarbon droplets from the continuous phase circulating hydrogen to obtain a dehydrogenator (1) of a mixed phase of a heavy hydrocarbon phase and a sulfur-containing circulating hydrogen; The gas phase outlet (3) of the dehydrogenator (1) is connected to further separate the obtained mixed phase to remove the sulfide therein to obtain a sulfur-free circulating hydrogen desulfurization tower (2); In the desulfurization tower (2), the obtained sulfur-free circulating hydrogen is further separated to remove the amine liquid, thereby obtaining a purified recycle hydrogen deaminator (5).

5. Apparatus according to claim 4, characterized in that the deaminator (5) is selected from the group consisting of a gravity settling tank, a coalescer, and a hydrocyclone.

6. The apparatus according to claim 4 or 5, wherein the deaminator (5) recovers the amine liquid by a particle size of up to 5 micrometers, and the recovery of droplets larger than 10 micrometers is greater than 90%. , the separation time is 1-3 seconds.

7. The apparatus according to claim 4, wherein when the hydrocarbon component in the dehydrogenator (1) is a hydrocarbon of C5 or higher, the calculated separation precision of the droplet is 3 micrometers, and is 5 micrometers or more. The removal rate of droplets exceeds 95%; the droplet separation precision for liquid hydrocarbons, diesel oil, and sulfur-containing sewage is 15 micrometers, and the removal rate of droplets of 25 micrometers or more exceeds 95%; The pressure drop is less than 0.15 MPa.

8. The apparatus according to claim 4, wherein when the dehydrogenator (1) is imported with heavy hydrocarbons When the amount is not more than 1350 mg/m ³ , the heavy hydrocarbon content at the outlet of the bottom flow port (4) is a trace amount.

9. The apparatus according to claim 4, further comprising a screen eliminator added in front of the deaminator (5) for preliminary removal of the tower entering the desulfurization tower (2) Part of the droplets and solid particles in the mixture in the top-mounted cyclone separator.

10. The apparatus according to claim 4, wherein the rich amine solution of the desulfurization tower (2) is discharged from the bottom effusion chamber into the amine liquid regeneration tower, and the lean amine from the regeneration tower is mixed with the supplementary amine. Driving into the desulfurization tower

(2) In the recycling, the amine consumption is reduced by 60%.