CN109401805A - A kind of renewable hydrargyrum-removing technology method of natural gas - Google Patents
A kind of renewable hydrargyrum-removing technology method of natural gas Download PDFInfo
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- CN109401805A CN109401805A CN201811558105.3A CN201811558105A CN109401805A CN 109401805 A CN109401805 A CN 109401805A CN 201811558105 A CN201811558105 A CN 201811558105A CN 109401805 A CN109401805 A CN 109401805A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
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- C—CHEMISTRY; METALLURGY
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B43/00—Obtaining mercury
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
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Abstract
The invention discloses a kind of renewable hydrargyrum-removing technology methods of natural gas, belong to natural gas purification field.The present invention uses the renewable demercuration molecular sieve of AgA (A type molecular sieve of loaded Ag), first preprocessed separation removal free water, liquid hydrocarbon and mechanical admixture, then pass through the adsorption-regeneration cycles step of absorption, reversed heating regeneration and positive cooling regeneration etc., the continuous demercuration process of natural gas, purified natural gas mercury content≤10ng/Nm of acquisition can be realized3.The technique solves the problems, such as regeneration gas insufficient pressure, power-equipment compressor need not be configured, investment and operating cost are lower, and non-renewable demercuration unit need not be added again, avoid subsequent processing problem of the non-renewable type mercury removal agent as mercurous dangerous waste, it is final to obtain liquid mercury product, realize the recycling of Hg in natural gas resource.
Description
Technical field
The invention belongs to natural gas purification fields, and in particular to a kind of renewable hydrargyrum-removing technology method of natural gas, by day
Recycling obtains liquid mercury product while mercury removal in right gas.
Background technique
Natural gas to China's energy structure optimizing and realizes carbon emission reduction target as a kind of efficient, clean green energy resource
It is of great significance.According to the difference of geological conditions, the natural gas largely produced both at home and abroad is more or less to be contained again
Mercury metal, content are generally 1000 ~ 200000ng/m3, the country also has the natural gas mercury content of some areas to be more than
1000000ng/m3.In the subsequent processing process of natural gas, mercury can be caused cryogenic heat exchange equipment, instrument and pipeline etc. seriously
Corrosion, once corrosion leakage easily causes serious production accident, the mercury in addition deposited in device can be to operator and maintenance
Worker causes personal safety to threaten problem, and natural gas as the mercury after fuel combustion enter atmosphere also and will will cause it is serious
Mercury environmental pollution.In consideration of it, to guarantee natural gas following process, conveying and the safety utilized, it is necessary to by the huge sum of money in natural gas
Belong to mercury effectively to be removed.
For the removing of Hg in natural gas, absorption method demercuration is mainly used in engineering.According to the difference of absorption principle, divide
For non-renewable demercuration and renewable demercuration technology, the former using sulfur loading active carbon or supported metal sulphide aluminium oxide as adsorbent,
The latter is using silver molecular sieve as adsorbent.Corresponding chemical reaction mechanism is as follows.
According to the difference of hydrargyrum-removing technology position, moisture demercuration and dry gas demercuration can be divided into.Moisture demercuration is natural in raw material
Gas carries out demercuration under the conditions of containing saturated water and saturated hydrocarbons.Compared with non-renewable demercuration, renewable demercuration can be will be natural
Recycling obtains liquid mercury product while mercury removal in gas, and renewable mercury removal agent reaches hardly mercurous after service life, no
Extra process is needed, and non-renewable mercury removal agent Adsorption of Mercury needs to be further processed as mercurous dangerous waste after reaching service life,
It is more complex to handling, storage, transport and treatment process.
United States Patent (USP) US5354357 discloses a kind of renewable hydrargyrum-removing technology, for mercury content >=2.0 μ g/Nm3Raw material
Gas, the composite bed formed using NaA dehydration molecular sieve and AgX silver molecular sieve, room temperature absorption, regeneration gas reversely heat regeneration
Realize renewable demercuration, the mercurous regeneration gas that desorption and regeneration goes out first goes out part water, liquid hydrocarbon through gas-liquid separation after cooler is cooling
With liquid mercury etc., last regeneration gas returns to unstripped gas after further removing mercury by non-renewable type mercury removal agent after compressor pressurizes
Entrance.It is obvious that the technique haves the shortcomings that two, first is that causing regeneration gas pressure ratio material pressure because adsorption bed has pressure drop
Power is low, and regeneration gas needs that unstripped gas entrance could be returned after compressor pressurizes, and undoubtedly increases operation energy consumption；Second is that regeneration gas
In uncooled gaseous mercury there is still a need for being further processed by non-renewable type mercury removal agent, be equivalent to and most of mercury carried out
Second adsorption not only increases investment in this way, but also still suffers from and need to regularly replace non-renewable type mercury removal agent and its bring
The problem of useless mercury removal agent is as the processing of dangerous waste object.
Summary of the invention
For various disadvantages existing for above-mentioned prior art technology, the present invention is intended to provide a kind of simple process, investment it is small,
Operation energy consumption is low and realizes the renewable hydrargyrum-removing technology method of natural gas of lossless, the unpowered return of regeneration gas.
To achieve the above object, the present invention provides a kind of renewable hydrargyrum-removing technology method of natural gas, the process packet
Include following processing step:
(1) pretreatment: going out free water and liquid hydrocarbon through unstripped gas gas-liquid separator separates from mercurous natural gas out-of-bounds and can
A small amount of mechanical admixture etc. existing for energy；
(2) adsorb: pretreated mercurous natural gas is divided into two-way, and the pressure of two-way, the first via are controlled by two regulating valves
Gas is as unstripped gas, and for the second road gas as regeneration gas, wherein first via gas, which is entered by four-way valve from tower top, is in adsorbed state
Adsorption tower carry out adsorption dewatering, demercuration, dehydrated adsorbent and demercuration adsorbent selective absorption removing effect under (contain
Water and mercury in mercury natural gas are successively dehydrated adsorbent and demercuration adsorbent absorption, and dehydrated adsorbent is upper mounted in adsorption tower
Layer, first water adsorbing and removing, then for the demercuration adsorbent of lower layer again mercury adsorbing and removing, the adsorption tower being detailed in Fig. 1 has two
Layer), purified natural gas can be obtained from tower bottom, send out battery limit (BL) after then passing sequentially through four-way valve and product gas regulating valve；
(3) stop absorption: with the progress of absorption, the mercury content in purified natural gas is gradually risen until reaching technical indicator value
(for technical indicator value generally there are two types of requirement, one is reach the defeated index request mercury content≤28000ng/Nm of natural gas tube3, separately
One is reach liquefied natural gas to index request≤10ng/Nm of mercury content3, technical indicator value that this place is said is≤
10ng/Nm3), absorption forward position reaches adsorption column outlet end, stops absorption immediately, switches four-way valve, is transferred to regeneration technology process；
(4) reversed heating regeneration: above-mentioned second road gas enters pretreatment adsorption tower by four-way valve, first to the pretreatment adsorption tower
Carry out positive cooling regeneration, after cooling, then be dehydrated and the selective absorption removing of demercuration adsorbent effect under, by the
Two road gas are dehydrated, demercuration processing, obtain regeneration gas of the second road gas of purification as adsorption tower from tower bottom, the regeneration gas into
Enter the reversed heating regeneration of adsorption tower progress for being in reproduced state from tower bottom by four-way valve after entering heater heating, with temperature
The raising of degree, water, the mercury adsorbed on adsorbent desorb, obtain desorption and regeneration gas from tower top and pass sequentially through two four-way valves
Enter cooler afterwards to cool down, then goes out liquid water and mercury, uncooled desorption and regeneration gas by regeneration gas gas-liquid separator separates
It returns again to and enters the adsorption tower in adsorbed state after mixing with first via gas；
(5) positive cooling regeneration: after the completion of aforementioned reversed heating regenerative process, switch four-way valve, pass sequentially through the second road gas
Two four-way valves enter the adsorption tower in the state of cooling, carry out positive cold blowing regeneration, and the regeneration gas come out from tower bottom passes through
Four-way valve enters heater heating, then enters pretreatment adsorption tower from bottom and carry out reversed heating regeneration to the tower, and pretreatment is inhaled
The regeneration gas that attached column overhead comes out enters cooler cooling after passing through four-way valve again, then passes through regeneration gas gas-liquid separator separates
Liquid water and mercury out, uncooled regeneration gas is returned again to mixed with first via gas after enter in adsorbed state adsorption tower.
By process above step, absorption-regeneration cycle is completed, thus realize natural gas continuous dehydration, demercuration process,
Purified natural gas can be met to mercury content (≤10ng/Nm3) requirement.
Further, the adsorption tower includes at least two adsorption tower and 1 pretreatment adsorption tower, and 2 adsorption towers alternately make
With realization continuous feed separates demercuration.
Further, dehydrated adsorbent is loaded on the upper layer of the adsorption tower, and renewable demercuration adsorbent loads in lower layer, takes off
The mass ratio of water absorbent and demercuration adsorbent is 1:0.1 ~ 1:0.5.
Further, the flow-rate ratio of the first via gas and the second road gas is 3:1 ~ 15:1.
Further, pressure high 10 ~ 150kPa of the pressure of second road gas compared with first via gas.
Further, the dehydrated adsorbent is NaA molecular sieve or activated alumina.
Further, the demercuration adsorbent be AgA molecular sieve (A type molecular sieve of loaded Ag), silver content be 0.1 ~
10wt%。
Further, the four-way valve includes at least 3, is respectively used to the mercurous natural gas of raw material, regeneration gas, purification naturally
The switching of gas.
Further, the heater heating exit temperature degree is 230 ~ 320 DEG C, guarantees dehydrated adsorbent and demercuration absorption
Agent can regenerate sufficiently.
Further, the cooler coolant outlet temperature degree is -20 ~ 50 DEG C.
The invention has the following advantages that
(1) the subsequent place of mercurous dangerous waste is avoided compared with non-renewable demercuration adsorbent using renewable demercuration adsorbent
Reason；
(2) renewable hydrargyrum-removing technology is used, solves the problems, such as regeneration gas insufficient pressure, without configuration power-equipment compression
Machine, investment and operating cost are lower；
(3) mercury in regeneration gas need not be handled using non-renewable type demercuration adsorbent, directly be mixed with the mercurous natural gas of raw material,
It is final to obtain liquid mercury product；
(4) mercury content≤10ng/Nm of purified natural gas3, reach depth demercuration technical requirements.
Detailed description of the invention
Fig. 1 is the renewable hydrargyrum-removing technology flow chart of natural gas of the present invention.
In figure, 1 is unstripped gas gas-liquid separator, and 2 be first via gas regulating valve, and 3 be adsorption tower, and 4 be adsorption tower, and 5 be pre-
Adsorption tower is handled, 6 be heater, and 7 be cooler, and 8 be regeneration gas gas-liquid separator, and 9 be the second road gas regulating valve, and 10 be four-way
Valve, 11 be four-way valve, and 12 be four-way valve, and 13 be product gas regulating valve.
Specific embodiment
Below by the drawings and specific embodiments, present invention is further described in detail.
As shown in Fig. 1, the renewable hydrargyrum-removing technology method of a kind of natural gas provided by the invention, specifically includes following technique
Step:
(1) pretreatment: isolating free water and liquid hydrocarbon through unstripped gas gas-liquid separator 1 from mercurous natural gas out-of-bounds and can
A small amount of mechanical admixture etc. existing for energy.
(2) adsorb (A): pretreated mercurous natural gas is divided into two-way, passes through first via gas regulating valve 2 and the second road gas
Regulating valve 9 controls the pressure of the first and second road gas respectively, first via gas as unstripped gas, the second road gas as regeneration gas,
Middle first via gas enters the adsorption tower 3 in adsorbed state from tower top by four-way valve 10 and carries out adsorption dewatering, demercuration, is being dehydrated
Under the selective absorption removing effect of adsorbent and demercuration adsorbent, purified natural gas can be obtained from tower bottom, is then successively led to
Battery limit (BL) is sent out after crossing four-way valve 11 and product gas regulating valve 13.
(3) stop absorption: with the progress of absorption, the mercury content in purified natural gas, which gradually rises until reaching technology, to be referred to
Scale value, absorption forward position reach adsorption column outlet end, stop absorption immediately, switch four-way valve, be transferred to adsorbent reactivation.
(4) reversed heating regeneration (D): above-mentioned second road gas enters pretreatment adsorption tower 5 by four-way valve 12, first pre- to this
Processing adsorption tower 5 carries out positive cooling regeneration, after cooling, then removes in dehydration and the selective absorption of demercuration adsorbent
Under effect, the second road gas is dehydrated, demercuration processing, obtains regeneration of the second road gas of purification as adsorption tower 3 from tower bottom
Gas, which, which enters after heater 6 heats, is carried out instead by four-way valve 11 from tower bottom into the adsorption tower 3 in reproduced state
It is regenerated to heating, as the temperature rises, water, the mercury adsorbed on adsorbent desorbs, and obtains desorption and regeneration gas simultaneously from tower top
Enter the cooling of cooler 7 after passing sequentially through four-way valve 10 and four-way valve 12, liquid is then isolated by regeneration gas gas-liquid separator 8
State water and mercury, uncooled desorption and regeneration gas is returned again to mixed with first via gas after enter in adsorbed state adsorption tower 4.
(5) positive cooling regeneration (C): after the completion of aforementioned reversed heating regenerative process, switch four-way valve 12, make the second road gas
It passes sequentially through four-way valve 12 and four-way valve 10 enters the adsorption tower 3 for being in the state of cooling, positive cold blowing regeneration is carried out, from tower bottom
Regeneration gas out passes through four-way valve 11 and enters the heating of heater 6, then enters pretreatment adsorption tower 5 from bottom and carry out instead to the tower
It is regenerated to heating, the regeneration gas that pretreatment 5 tower top of adsorption tower comes out cools down after passing through four-way valve 12 again into cooler 7, then
Isolate liquid water and mercury by regeneration gas gas-liquid separator 8, uncooled regeneration gas return again to mixed with first via gas it is laggard
Enter to be in the adsorption tower 4 of adsorbed state.
By process above step, absorption-regeneration cycle is completed, thus realize natural gas continuous dehydration, demercuration process,
Purified natural gas can be met to mercury content (≤10ng/Nm3) requirement.
Using the renewable hydrargyrum-removing technology process of natural gas shown in Fig. 1, the mercurous gas pressure of raw material is 10.5MPa.G, temperature
20 ~ 40 DEG C of degree, flow 100 × 104Nm3/ d, composition are as shown in table 1.
The mercurous gas component of 1 raw material of table forms table
。
The preprocessed separation removal free water of the mercurous natural gas of raw material and liquid hydrocarbon and a small amount of mechanical admixture that may be present
Deng after, into adsorption tower in adsorption dewatering, demercuration, each adsorption tower undergoes absorption as shown in table 2 below-regeneration cycle technique
Step, to realize natural gas continuous dehydration, demercuration process.
2 absorption of table-regeneration cycle processing step table
。
Remarks: A represents absorption, and D represents reversed heating regeneration, and C represents positive cooling regeneration.
Dehydrated adsorbent NaA molecular sieve is loaded on the upper layer of above-mentioned adsorption tower, and renewable demercuration absorption is loaded by lower layer
Agent AgA molecular sieve, the mass ratio of the two are 1:0.35.First via gas and the second tunnel throughput ratio are 7:1, and the second road gas
Pressure high 50 ~ 80kPa of the pressure compared with first via gas.When reversed heating regeneration, heater heating exit temperature degree is 260 ~ 280
DEG C, guarantee that dehydrated adsorbent and demercuration adsorbent can regenerate sufficiently, cooler coolant outlet temperature degree is 10 ~ 30 DEG C.
After above-mentioned process, mercury content can take off to 10ng/Nm in purified natural gas3Hereinafter, meeting liquefied natural gas
(LNG) to the technical requirements of mercury content, recycling obtains liquid mercury product while effectively removing mercury, realizes returning for mercury resource
It receives.
Above-described embodiment is only representative example of the invention, the implementation and power being not intended to limit the invention
Sharp range, all technical solutions identical or equivalent with content described in the claims in the present invention should all be included in present invention protection model
In enclosing.
Claims (10)
1. a kind of renewable hydrargyrum-removing technology method of natural gas, which is characterized in that the process the following steps are included:
(1) it pre-processes: going out free water, liquid hydrocarbon and a small amount of through unstripped gas gas-liquid separator separates from mercurous natural gas out-of-bounds
Mechanical admixture；
(2) adsorb: pretreated mercurous natural gas is divided into two-way, and the pressure of two-way, the first via are controlled by two regulating valves
Gas is as unstripped gas, and for the second road gas as regeneration gas, wherein first via gas, which is entered by four-way valve from tower top, is in adsorbed state
Adsorption tower carry out adsorption dewatering, demercuration, dehydrated adsorbent and demercuration adsorbent selective absorption removing effect under
Purified natural gas is obtained from tower bottom, sends out battery limit (BL) after then passing sequentially through four-way valve and product gas regulating valve；
(3) stop absorption: with the progress of absorption, the mercury content in purified natural gas is gradually risen until reaching technical indicator
Value, absorption forward position reach adsorption column outlet end, stop absorption immediately, switch four-way valve, be transferred to regeneration technology process；
(4) reversed heating regeneration: above-mentioned second road gas enters pretreatment adsorption tower by four-way valve, first to the pretreatment adsorption tower
Carry out positive cooling regeneration, after cooling, then be dehydrated and the selective absorption removing of demercuration adsorbent effect under, by the
Two road gas are dehydrated, demercuration processing, obtain regeneration gas of the second road gas of purification as adsorption tower from tower bottom, the regeneration gas into
Enter the reversed heating regeneration of adsorption tower progress for being in reproduced state from tower bottom by four-way valve after entering heater heating, with temperature
The raising of degree, water, the mercury adsorbed on adsorbent desorb, obtain desorption and regeneration gas from tower top and pass sequentially through two four-way valves
Enter cooler afterwards to cool down, then goes out liquid water and mercury, uncooled desorption and regeneration gas by regeneration gas gas-liquid separator separates
It returns again to and enters the adsorption tower in adsorbed state after mixing with first via gas；
(5) positive cooling regeneration: after the completion of aforementioned reversed heating regenerative process, switch four-way valve, pass sequentially through the second road gas
Two four-way valves enter the adsorption tower in the state of cooling, carry out positive cold blowing regeneration, and the regeneration gas come out from tower bottom passes through
Four-way valve enters heater heating, then enters pretreatment adsorption tower from bottom and carry out reversed heating regeneration to the tower, and pretreatment is inhaled
The regeneration gas that attached column overhead comes out enters cooler cooling after passing through four-way valve again, then passes through regeneration gas gas-liquid separator separates
Liquid water and mercury out, uncooled regeneration gas is returned again to mixed with first via gas after enter in adsorbed state adsorption tower.
2. the renewable hydrargyrum-removing technology method of natural gas according to claim 1, the adsorption tower includes at least two adsorption tower
With 1 pretreatment adsorption tower, 2 adsorption towers are used alternatingly, and realize that continuous feed separates demercuration.
3. dehydration is loaded on the upper layer of the renewable hydrargyrum-removing technology method of natural gas according to claims 1 and 2, the adsorption tower
The mass ratio of adsorbent, the renewable demercuration adsorbent of lower layer's filling, dehydrated adsorbent and demercuration adsorbent is 1:0.1 ~ 1:
0.5。
4. the renewable hydrargyrum-removing technology method of natural gas according to claim 1, the stream of the first via gas and the second road gas
Amount is than being 3:1 ~ 15:1.
5. the renewable hydrargyrum-removing technology method of natural gas according to claim 1, the pressure of second road gas is compared with the first via
High 10 ~ the 150kPa of the pressure of gas.
6. the renewable hydrargyrum-removing technology method of natural gas according to claim 1 or 3, the dehydrated adsorbent is NaA molecule
Sieve or activated alumina.
7. the renewable hydrargyrum-removing technology method of natural gas according to claim 1 or 3, the demercuration adsorbent is AgA molecule
Sieve, silver content are 0.1 ~ 10wt%.
8. the renewable hydrargyrum-removing technology method of natural gas according to claim 1, the four-way valve includes at least 3, respectively
Switching for raw material mercurous natural gas, regeneration gas, purified natural gas.
9. the renewable hydrargyrum-removing technology method of natural gas according to claim 1, the heater heating exit temperature degree are
230 ~ 320 DEG C, guarantee that dehydrated adsorbent and demercuration adsorbent can regenerate sufficiently.
10. the renewable hydrargyrum-removing technology method of natural gas according to claim 1, the cooler coolant outlet temperature degree
It is -20 ~ 50 DEG C.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110559793A (en) * | 2019-09-29 | 2019-12-13 | 河北石兴科技有限公司 | Novel method for removing mercury from renewable natural gas |
| CN113493709A (en) * | 2020-04-01 | 2021-10-12 | 中国石油天然气股份有限公司 | Under-saturated natural gas moisture demercuration device |
| CN114062414A (en) * | 2020-08-07 | 2022-02-18 | 中国石油化工股份有限公司 | Mercury collecting and quantifying method and collecting system in gas generation process of thermal simulation experiment |
| CN114106895A (en) * | 2020-08-25 | 2022-03-01 | 中国石油天然气股份有限公司 | Hot-blowing dry type natural gas moisture demercuration device and method |
| CN115216350A (en) * | 2021-04-20 | 2022-10-21 | 中国石油工程建设有限公司 | Moisture regeneration demercuration system and method for obtaining product gas with ultra-low mercury concentration |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110559793A (en) * | 2019-09-29 | 2019-12-13 | 河北石兴科技有限公司 | Novel method for removing mercury from renewable natural gas |
| CN113493709A (en) * | 2020-04-01 | 2021-10-12 | 中国石油天然气股份有限公司 | Under-saturated natural gas moisture demercuration device |
| CN114062414A (en) * | 2020-08-07 | 2022-02-18 | 中国石油化工股份有限公司 | Mercury collecting and quantifying method and collecting system in gas generation process of thermal simulation experiment |
| CN114062414B (en) * | 2020-08-07 | 2024-05-07 | 中国石油化工股份有限公司 | Method and system for collecting and quantifying mercury in thermal simulation experiment gas generating process |
| CN114106895A (en) * | 2020-08-25 | 2022-03-01 | 中国石油天然气股份有限公司 | Hot-blowing dry type natural gas moisture demercuration device and method |
| CN115216350A (en) * | 2021-04-20 | 2022-10-21 | 中国石油工程建设有限公司 | Moisture regeneration demercuration system and method for obtaining product gas with ultra-low mercury concentration |
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