CN105347311A - Method used for generating elemental sulfur via selective oxidation of H2S - Google Patents

Method used for generating elemental sulfur via selective oxidation of H2S Download PDF

Info

Publication number
CN105347311A
CN105347311A CN201510814964.4A CN201510814964A CN105347311A CN 105347311 A CN105347311 A CN 105347311A CN 201510814964 A CN201510814964 A CN 201510814964A CN 105347311 A CN105347311 A CN 105347311A
Authority
CN
China
Prior art keywords
selective oxidation
elemental sulfur
air
processing method
road
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510814964.4A
Other languages
Chinese (zh)
Other versions
CN105347311B (en
Inventor
胡文宾
崔国栋
王强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SHANDONG XUNDA CHEMICAL GROUP CO Ltd
Original Assignee
SHANDONG XUNDA CHEMICAL GROUP CO Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SHANDONG XUNDA CHEMICAL GROUP CO Ltd filed Critical SHANDONG XUNDA CHEMICAL GROUP CO Ltd
Priority to CN201510814964.4A priority Critical patent/CN105347311B/en
Publication of CN105347311A publication Critical patent/CN105347311A/en
Application granted granted Critical
Publication of CN105347311B publication Critical patent/CN105347311B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
    • C01B17/0426—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the catalytic conversion

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention provides a method used for generating elemental sulfur via selective oxidation of H2S. A device of the method comprises a heater, a selective oxidation reactor, a middle temperature condenser, a low temperature condenser, and a molten sulphur groove; the selective oxidation reactor is filled with 5 to 12% of a Fe2O3/silicon oxide H2S selective oxidation catalyst with an average pore diameter ranging from 30 to 50nm in a plurality of layers, an air spray inlet and a cooling coil pipe is arranged between each pair of layers respectively; the temperature of the catalyst layers, air adding total amount, and air distribution amount at each air spray inlet are controlled to be appropriate so as to realize complete oxidation of H2S in a process gas containing 0.5 to 2% H2S, SO2 with a concentration of 200mg/m<3> or lower is generated, the other element sulfur is conversed into elemental sulfur, and strict discharge standards of the industry or the area are satisfied. Technological process is short and simple; SO2 emission concentration is low; and technology operation is stable.

Description

H 2s selective oxidation generates the processing method of elemental sulfur
Technical field
The present invention relates to a kind of recovery technology of sulfur method, be specifically related to a kind of H 2s selective oxidation generates the processing method of elemental sulfur.
Background technology
In petrochemical complex, Coal Chemical Industry, coal gasification course, a part of sulphur contained by raw material can change into H usually 2s, is formed containing H through being separated 2the sour gas of S, this sour gas generally processes through recovery technology of sulfur, by H 2s is converted into elemental sulfur as much as possible.
Recovery technology of sulfur device, in operation process, through the tail gas that chimney is emptying, its SO 2concentration is continuous monitoring project, although the higher limit of existing discharge standard of air pollutants GB16297-1996 is as 700mg/m 3be not difficult to reach, but also may there is more strict emission standard in place industry or location; H 2s is one of odor pollution material included by emission standard for odor pollutants GB14554-93, and emission limit is more strict, the accurate higher limit of factory's boundary mark as three grades be 0.45/0.80mg/m 3, 100 meters of smoke stack emission amount higher limits are 14kg/h.
Along with the raising of environmental protection standard, increasingly strict to the requirement of recovery technology of sulfur tail gas, thus, when the recovery technology of sulfur of pre-treatment sour gas, its back segment often comprises H 2the step of S selective oxidation, will come from the lower H as 0.5-2% of content in preceding step Process Gas 2s, and the O allocated into 2reaction, selective oxidation generates elemental sulfur.
H 2s selective oxidation reaction, object product is elemental sulfur, is separated and enters liquid-state sulfur groove, finally form sulfur product; Side reaction is SO 2.Usually to H in tail gas 2s, SO 2the requirement of content is generally as far as possible not containing H 2s, SO 2content is as far as possible low, thus, if do not have other treatment step directly to discharge as steps such as catalyzed oxidation adsorption desulfurizes after selective oxidation, then and should at H 2s selective oxidation step is by H 2s transforms entirely, is converted into elemental sulfur as much as possible, reduces SO simultaneously as far as possible 2selectivity.
H 2s selective oxidation generates in the reaction of elemental sulfur, reduces by product SO 2optionally method, except suitable control O 2the amount of allocating into and temperature of reaction, also to adopt the Fe that the active lower catalyzer of Crouse is as larger in aperture 2o 3/ silicon oxide catalyst, but at guarantee H 2while S transforms entirely, prior art not easily accomplishes SO 2content is lower than 200mg/m 3and even 100mg/m 3, 50mg/m 3level, thus not easily reach place industry or area may exist comparatively strict emission standard.
Summary of the invention
For overcoming above-mentioned technological deficiency, the invention provides a kind of H 2s selective oxidation generates the processing method of elemental sulfur, for the treatment of containing H 2the process gas of S0.5-2%, at guarantee H 2while S transforms entirely, make SO 2content is lower than 200mg/m 3and even 100mg/m 3, 50mg/m 3, thus reach place industry or area may exist comparatively strict emission standard.
Technical scheme of the present invention is: a kind of H 2s selective oxidation generates the processing method of elemental sulfur, comprises well heater, selective oxidation reaction device, middle temperature condenser and subcooling condenser, Molten sulphur groove; The 5-12%Fe of average pore diameter 30-50nm is loaded in reactor 2o 3/ silicon oxide H 2s catalyst for selective oxidation, catalyzer divides multilayer to load, interlayer Ge She mono-road air entrance and a road temperature-reducing coil; By suitably control each reaction bed temperature, air allocate total amount and the sendout at each gas inlet into, by the H in Process Gas 2s is all oxidized, except generation≤200mg/m 3sO 2, all the other are all converted into elemental sulfur;
Containing H 2the unstripped gas of S volume content 0.5-2%, and measure the air mixed allocated into, after heater via is preheating to 180 ~ 210 DEG C, enter selective oxidation reaction device by top, between catalyst layer, entrance sprays into the air of metering; Regulate the air capacity of each bed and coil pipe cooling degree, control middle and upper part bed temperature 180-220 DEG C, bottom bed temperature 220-240 DEG C, not containing H in making to work off one's feeling vent one's spleen 2s, SO 2volume content≤200mg/m 3; Work off one's feeling vent one's spleen and enter middle temperature condenser, be cooled to 140-160 DEG C, the elemental sulfur of generation is separated and enters Molten sulphur groove, and middle temperature condenser overhead is worked off one's feeling vent one's spleen, then is cooled to after the 40-60 DEG C of micro-elemental sulfur of removing residue through subcooling condenser, emptying through chimney.
H of the present invention 2s selective oxidation generates in the processing method of elemental sulfur, and preferably, selective oxidation reaction device inner catalyst divides 4-10 layer to load, and interlayer establishes 3-9 road gas inlet, together with the gas inlet allocating unstripped gas before well heater into, establishes 4-10 road gas inlet altogether.
H of the present invention 2s selective oxidation generates in the processing method of elemental sulfur, preferably, air entrance set by selective oxidation reaction device inner catalyst interlayer, there is high speed spout, supersonic speed spout is better, more preferably every road gas inlet has multiple mouths, to enable sprayed into air and Process Gas mix better faster, described high speed spout, supersonic speed spout have the jet size matched with air straying quatity.
H of the present invention 2s selective oxidation generates the processing method of elemental sulfur, has the following advantages:
1) technique is comparatively brief, SO 2emission concentration is lower
The 5-12%Fe of average pore diameter 30-50nm is loaded in reactor 2o 3/ silicon oxide H2S catalyst for selective oxidation, and catalyzer divides multilayer to load, interlayer Ge She mono-road air entrance and a road temperature-reducing coil; By suitably control each reaction bed temperature, air allocate total amount and the sendout at each gas inlet into, make temperature of reaction lower, make O in reactant gases 2concentration lower, thus while being all oxidized by the H2S in Process Gas, achieve lower SO 2generation, all the other are all converted into elemental sulfur, SO in emptying tail gas 2content is lower than 200mg/m 3and even 100mg/m 3, 50mg/m 3, not containing other sulfide, thus reach place industry or area may exist comparatively strict emission standard; Fe used 2o 3it is active that/silicon oxide catalyst has lower Crouse, is a key;
2) process runs well
In reactor load Fe 2o 3/ silicon oxide catalyst, can give play to selective oxidation H in longer operational process 2s generates the stability of elemental sulfur, and reason is the stability of its silica support, the average pore diameter of catalyzer 30-50nm and the low O of low temperature 2fe under condition 2o 3not easily there is the character of sulphating: silica support acid resistance, water tolerance are better, not by H under 180 ~ 240 DEG C of temperature of reaction conditions 2s, SO 2erosion; Catalyzer there is the average pore diameter of 30-50nm, make the liquid sulfur that formed in internal gutter less, the blocking formed is less; At the low O of the low temperature of this processing method 2under condition, the Fe of catalyzer 2o 3active ingredient can in the operation of several years less generation sulphating.
Accompanying drawing explanation
Accompanying drawing 1 is H of the present invention 2s selective oxidation generates the concise and to the point flow process of the processing method of elemental sulfur, and wherein device numbering is followed successively by 1 well heater, 2 selective oxidation reaction devices, warm condenser in 3,4 subcooling condensers, 5 Molten sulphur grooves, 6 chimneys.
Embodiment
Embodiment 1
A set of sulfur recovery facility, comprises well heater, selective oxidation reaction device, middle temperature condenser and subcooling condenser, Molten sulphur groove; Selective oxidation reaction device filling Fe 2o 3/ silicon oxide H 2s catalyst for selective oxidation 60m 3, catalyzer divides 6 layers respectively to fill 10m 3, interlayer Ge She mono-road gas inlet and temperature-reducing coil, every road air has 5 high speed spouts; Described Fe 2o 3/ silicon oxide catalyst Fe 2o 3content 5%, average pore diameter 50nm, profile is the column-shape strip of Ф 3x5-10mm; The elementary operation condition of this device is:
Unstripped gas 20000m 3/ hr, H 2s volume content 0.5%, all the other are N mainly 2, CO 2, COS≤20mg/m 3, without other sulfide, allocate air total amount 250m into 3about/hr reacts; Unstripped gas allocates 70m into 3the air of about/hr, enters selective oxidation reaction device by top after being preheating to 210 DEG C, all the other 180m 3the air of about/hr distributes between 5 road entrances between catalyst layer, and metering sprays into; Regulate the air capacity of each bed and coil pipe cooling degree, control upper part 3 bed temperature 210-220 DEG C, lower part 3 bed temperature 230-240 DEG C, not containing H in making to work off one's feeling vent one's spleen 2s, SO 2volume content≤100mg/m 3, not containing other sulfide; Work off one's feeling vent one's spleen and enter middle temperature condenser, be cooled to 150 DEG C, the elemental sulfur of generation is separated and enters Molten sulphur groove; Middle temperature condenser overhead is worked off one's feeling vent one's spleen, and is cooled to 40 DEG C of micro-elemental sulfurs of removing residue through subcooling condenser, emptying through chimney.
This sulfur recovery facility, in 1 year that puts into operation, this sulfur recovery facility smooth running, not containing H in air-discharging 2s, SO 2volume content≤100mg/m 3, wherein most of the time≤50mg/m 3, not containing other sulfide.
Embodiment 2
A set of sulfur recovery facility, comprises well heater, selective oxidation reaction device, middle temperature condenser and subcooling condenser, Molten sulphur groove; Selective oxidation reaction device filling Fe 2o 3/ silicon oxide H 2s catalyst for selective oxidation 50m 3, catalyzer divides 8 layers respectively to fill 6.25m 3, interlayer Ge She mono-road gas inlet and temperature-reducing coil, every road air has 5 high speed spouts; Described Fe 2o 3/ silicon oxide catalyst Fe 2o 3content 12%, average pore diameter 30nm, profile is the column-shape strip of Ф 3x5-10mm; The elementary operation condition of this device is:
Unstripped gas 10000m 3/ hr, H 2s volume content 1.8%, all the other are N mainly 2, CO 2, COS≤20mg/m 3, without other sulfide, allocate air total amount 450m into 3about/hr reacts; Unstripped gas allocates 100m into 3the air of about/hr, enters selective oxidation reaction device by top after being preheating to 180 DEG C, all the other 350m 3the air of about/hr distributes between 7 road entrances between catalyst layer, and metering sprays into; Regulate the air capacity of each bed and coil pipe cooling degree, control 5, middle and upper part bed temperature 200-220 DEG C, 3, bottom bed temperature 230-240 DEG C, not containing H in making to work off one's feeling vent one's spleen 2s, SO 2volume content≤100mg/m 3, not containing other sulfide; Work off one's feeling vent one's spleen and enter middle temperature condenser, be cooled to 150 DEG C, the elemental sulfur of generation is separated and enters Molten sulphur groove; Middle temperature condenser overhead is worked off one's feeling vent one's spleen, and is cooled to 60 DEG C of micro-elemental sulfurs of removing residue through subcooling condenser, emptying through chimney.
This sulfur recovery facility, in 1 year that puts into operation, this sulfur recovery facility smooth running, not containing H in air-discharging 2s, SO 2volume content≤100mg/m 3, wherein most of the time≤50mg/m 3, not containing other sulfide.

Claims (5)

1. a H 2s selective oxidation generates the processing method of elemental sulfur, comprises well heater, selective oxidation reaction device, middle temperature condenser and subcooling condenser, Molten sulphur groove; The 5-12%Fe of average pore diameter 30-50nm is loaded in reactor 2o 3/ silicon oxide H 2s catalyst for selective oxidation, catalyzer divides multilayer to load, interlayer Ge She mono-road air entrance and a road temperature-reducing coil; By suitably control each reaction bed temperature, air allocate total amount and the sendout at each gas inlet into, by the H in Process Gas 2s is all oxidized, except generation≤200mg/m 3sO 2, all the other are all converted into elemental sulfur;
Containing H 2the unstripped gas of S volume content 0.5-2%, and measure the air mixed allocated into, after heater via is preheating to 180 ~ 210 DEG C, enter selective oxidation reaction device by top, between catalyst layer, entrance sprays into the air of metering; Regulate the air capacity of each bed and coil pipe cooling degree, control middle and upper part bed temperature 180-220 DEG C, bottom bed temperature 220-240 DEG C, not containing H in making to work off one's feeling vent one's spleen 2s, SO 2volume content≤200mg/m 3; Work off one's feeling vent one's spleen and enter middle temperature condenser, be cooled to 140-160 DEG C, the elemental sulfur of generation is separated and enters Molten sulphur groove, and middle temperature condenser overhead is worked off one's feeling vent one's spleen, then is cooled to after the 40-60 DEG C of micro-elemental sulfur of removing residue through subcooling condenser, emptying through chimney.
2. H as claimed in claim 1 2s selective oxidation generates the processing method of elemental sulfur, and it is characterized in that, oxidation reactor inner catalyst divides 4-10 layer to load, and interlayer establishes 3-9 road gas inlet, together with the gas inlet allocating unstripped gas before well heater into, establishes 4-10 road gas inlet altogether.
3. H as claimed in claim 1 2s selective oxidation generates the processing method of elemental sulfur, and it is characterized in that, the air entrance set by selective oxidation reaction device inner catalyst interlayer, has high speed spout, and described high speed spout has the jet size matched with air straying quatity.
4. H as claimed in claim 3 2s selective oxidation generates the processing method of elemental sulfur, and it is characterized in that, described high speed spout is supersonic speed spout.
5. the arbitrary H as described in claim 1-4 2s selective oxidation generates the processing method of elemental sulfur, and it is characterized in that, the every road gas inlet set by selective oxidation reaction device inner catalyst interlayer has multiple mouths.
CN201510814964.4A 2015-11-23 2015-11-23 H2S selective oxidations generate the process of elemental sulfur Active CN105347311B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510814964.4A CN105347311B (en) 2015-11-23 2015-11-23 H2S selective oxidations generate the process of elemental sulfur

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510814964.4A CN105347311B (en) 2015-11-23 2015-11-23 H2S selective oxidations generate the process of elemental sulfur

Publications (2)

Publication Number Publication Date
CN105347311A true CN105347311A (en) 2016-02-24
CN105347311B CN105347311B (en) 2018-05-08

Family

ID=55323409

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510814964.4A Active CN105347311B (en) 2015-11-23 2015-11-23 H2S selective oxidations generate the process of elemental sulfur

Country Status (1)

Country Link
CN (1) CN105347311B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106698361A (en) * 2016-12-14 2017-05-24 山东迅达化工集团有限公司 Sulfur recycling process for acid gas
CN109789394A (en) * 2016-09-26 2019-05-21 雅各布斯荷兰有限公司 Improved catalyst for selective oxidation of sulfureted hydrogen

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1049320A (en) * 1989-07-21 1991-02-20 Veg气体研究所公司 Being used for selective oxidation sulfide becomes the catalyzer of elementary sulfur, and its method for making and selective oxidation sulfide become the method for elementary sulfur
CN1909950A (en) * 2004-01-15 2007-02-07 科诺科飞利浦公司 Process for the catalytic partial oxidation of h2s using staged addition of oxygen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1049320A (en) * 1989-07-21 1991-02-20 Veg气体研究所公司 Being used for selective oxidation sulfide becomes the catalyzer of elementary sulfur, and its method for making and selective oxidation sulfide become the method for elementary sulfur
CN1909950A (en) * 2004-01-15 2007-02-07 科诺科飞利浦公司 Process for the catalytic partial oxidation of h2s using staged addition of oxygen

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109789394A (en) * 2016-09-26 2019-05-21 雅各布斯荷兰有限公司 Improved catalyst for selective oxidation of sulfureted hydrogen
CN109789394B (en) * 2016-09-26 2022-03-01 沃利荷兰有限公司 Improved catalyst for selective oxidation of hydrogen sulfide
CN106698361A (en) * 2016-12-14 2017-05-24 山东迅达化工集团有限公司 Sulfur recycling process for acid gas
CN106698361B (en) * 2016-12-14 2019-04-05 山东迅达化工集团有限公司 The recovery technology of sulfur of sour gas

Also Published As

Publication number Publication date
CN105347311B (en) 2018-05-08

Similar Documents

Publication Publication Date Title
US8118284B2 (en) Collector-distributor combination
BR122018069706B1 (en) METHOD TO CONTROL AEROSOL PRODUCTION DURING ABSORPTION OF SULFUR DIOXIDE FROM A DISCHARGE GAS
US8128071B2 (en) Method and apparatus for improved gas/fluid contact
US20020192144A1 (en) Method for producing high-purity sulphuric acid
US20100139488A1 (en) Flue gas scrubbing apparatus and process
CN102698584B (en) Sectional absorption ammonia desulfurization process and device
CN105293444B (en) The recovery technology of sulfur of low-sulfur discharge
CN105347311A (en) Method used for generating elemental sulfur via selective oxidation of H2S
US9260307B2 (en) Catalytic sulfur degassing
CN105314607A (en) Low-sulfur discharging and sulfur recycling process of intermediate concentration acid gas
CN102908890A (en) Device for preventing ammonia escape in ammonia desulfurization and denitration of flue gases
CA1045787A (en) Process for decreasing the total sulfur content of claus off-gas
FI62002B (en) REFERENCE FITTING FOR SEPARATION OF A QUANTIFIED HYDRAULIC ACID WITH A GASER
CN106865959A (en) The circulation utilization method of 3D glass tin tank shielded gas
CN202654931U (en) Sectional absorption ammonia desulphurization device
EP1664353A1 (en) Method and system for granulating slag
CN101987976B (en) Desulfurizing tower for gas desulfuration by using liquid phase catalytic oxidation
CN102917772A (en) Flow control method and apparatus for a continuous multiple zone mass transfer
CN108434948A (en) A kind of acid gas absorbs oxidizing tower and its working method
CN204710090U (en) A kind of industrial fumes desulfurizing tower
CN101541397B (en) Washing column with reduced construction height
CN104061580B (en) Process ammonia desulfuration equipment and the technique thereof of flue gas desulfurization band liquid
EP2889075A1 (en) Plate arranged to support a bed of liquid absorbent in a device for purifying gas
EP4077212B1 (en) A venturi absorber tube for absorbing sulfur trioxide in sulfuric acid
CN104971600B (en) A kind of sour gas tubular reactor and handling process method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant