CN105819578B - One kind is used for MTO water scrubber scale removers - Google Patents
One kind is used for MTO water scrubber scale removers Download PDFInfo
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- CN105819578B CN105819578B CN201610243528.0A CN201610243528A CN105819578B CN 105819578 B CN105819578 B CN 105819578B CN 201610243528 A CN201610243528 A CN 201610243528A CN 105819578 B CN105819578 B CN 105819578B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- -1 Alkyl phenol Chemical compound 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 241001272567 Hominoidea Species 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims 2
- 229910021641 deionized water Inorganic materials 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 24
- 238000009833 condensation Methods 0.000 abstract description 22
- 230000005494 condensation Effects 0.000 abstract description 22
- 239000003054 catalyst Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000013618 particulate matter Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 208000006558 Dental Calculus Diseases 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- 239000000693 micelle Substances 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000003381 solubilizing effect Effects 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N c1ccccc1 Chemical compound c1ccccc1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000012962 cracking technique Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 1
- WZGWWPARMFQTAY-UHFFFAOYSA-N ethene;methanol Chemical compound OC.C=C WZGWWPARMFQTAY-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- YUWFEBAXEOLKSG-UHFFFAOYSA-N hexamethylbenzene Chemical compound CC1=C(C)C(C)=C(C)C(C)=C1C YUWFEBAXEOLKSG-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to water system scale removal field, to solve the problems, such as MTO water scrubbers anti-tartar and On Line Foul Removing Technology, the present invention proposes a kind of for MTO water scrubber scale removers, each component is put into vessel in heating to each component and is completely dissolved by scale remover, it is uniformly mixed, it is cooled to filter after room temperature and is made, the scale remover of the present invention prevents or reduced the possibility of high condensation point accessory substance and catalyst fines formation large particulate matter, simultaneously the high condensation point accessory substance for having formed dirty thing can also be promoted to be dissolved in the water, the online dirty thing removed in water scrubber.
Description
Technical field
The present invention relates to water system scale removal field, relate in particular to a kind of for MTO water scrubber scale removers.
Background technology
The low-carbon alkenes such as ethene, propylene are the core and industrial chemicals the most basic, especially ethene of petrochemical industry
Production capacity is to weigh one of mark of a countries and regions chemical industry level.Current main ethene, production of propylene mode are
Using oil as the cracking technique of raw material, such as naphtha steam cracking, heavy oil catalytic pyrolysis, ethane cracking.Yet with oil
Gradually decreasing for resource, the challenge of raw material supply anxiety will be faced using the production line of conventional petroleum raw material.Coal resources phase
To petroleum resources compared with horn of plenty, the consumption of petroleum resources can be greatly reduced through methanol ethene, propylene using coal.Methanol alkene
Hydrocarbon (MTO) technique is then to arise at the historic moment in this condition, shows huge potential advantages.
Reaction gas from methanol-to-olefins (MTO) device chilling tower enters water scrubber bottom, comes with water scrubber top
Washing water counter current contacting, carries out mass-and heat-transfer.The effect of water scrubber mainly has 3；One is by water vapor condensation in reaction gas；Two
It is to continue reaction gas to be cooled to compressor inlet temperature, while providing low-temperature heat source for separation of olefins unit；Three be that removing is anti-
A small amount of heavy hydrocarbon and oxygenates in answering.
In MTO courses of reaction, in addition to purpose product low-carbon alkene, also substantial amounts of water vapour, mixed alkanes, aromatic hydrocarbon,
The accessory substances such as coke.When reaction gas enters in water scrubber, temperature is reduced after heat exchange, and the accessory substance of high condensation point will be separated out,
When the high condensation point accessory substance and catalyst fines of precipitation are coexisted in water scrubber, high condensation point accessory substance plays bridging action and urged
Agent powder formation large particulate matter, blocks air vent channel, causes water scrubber tower pressure difference to raise, influence the normal fortune of water scrubber
OK, and then whole MTO normal operation is influenceed, the consequence such as serious meeting causes whole device to stop work.
At present, all it is using the catalyst powder in some rotary separators or filter membrane separation water scrubber such issues that solution
The method of last and high condensation point accessory substance.CN203820559U and CN103951098A disclose chilling and washing water in MTO techniques
The device of de- solid oil removing, catalyst fines and high condensation point accessory substance are reclaimed using Ultra filtration membrane method.These methods are all deposited
In limitation, if effect forms large particulate matter to high condensation point accessory substance between catalyst fines, and adhere to and blocked up
Plug is on tower passage.Separators all in the case is all helpless.
Up to the present, have no and remove what is formed on MTO washing towers online using the method for scale remover both at home and abroad
The report of dirty thing.
The content of the invention
To solve the problems, such as MTO water scrubbers anti-tartar and On Line Foul Removing Technology, the present invention proposes a kind of for MTO water scrubber scale removal
Agent, prevents or reduces the possibility of high condensation point accessory substance and catalyst fines formation large particulate matter, while can also promote to have tied
High condensation point accessory substance into dirty thing is dissolved in the water, the online dirty thing removed in water scrubber.
The present invention is achieved by the following technical solutions：One kind is used for MTO water scrubber scale removers, and scale remover is by following groups
Part is put into vessel in heating to each component and is completely dissolved, and is uniformly mixed, and is cooled to after room temperature and filters obtained, each component
Parts by weight are：
Preferably, the parts by weight of each component are：
The preparation method of the water scrubber scale remover of the present invention is simple heating mixed method, by AEO
The solubilized assistant agent of solubilizer, 2- nitro -4- APESs solubilizer, alkyl phenol polyethenoxy ether sodium sulfate and deionization
Water, is put into vessel in heating to each component and is completely dissolved, be uniformly mixed, be cooled to after room temperature, be filtrated to get.Described room
Temperature is 20~25 DEG C.
Described AEO solubilizer structural formula is such as shown in (I)：
RO(CH2CH2O)nH (I),
Wherein, R=C12~C18Integer between alkyl, n=15~40, preferably R=C12~C14Alkyl, n=15~30
Between integer.
Described 2- nitro -4- APES solubilizing agent molecules formula is such as shown in (II)：
Wherein, R1=C8~C18Integer between alkyl, m=15~40, preferably R1=C12~C14Alkyl, m=15~
Integer between 30.
The solubilized assistant agent molecular formula of described alkyl phenol polyethenoxy ether sodium sulfate is such as shown in (III)：
Wherein, R2=C12~C18Integer between alkyl, p=3~4, preferably R2=C16~C18Alkyl, p=3~4 it
Between integer.
Learnt according to the detection and analysis of MTO water scrubber tampers, water scrubber tamper is in addition to the catalyst of vast scale, also
It is the high condensation point accessory substance for playing bridge formation cementation, such as trimethylbenzene, durol and hexamethylbenzene to have part.This scale removal
Agent scale removal principle is to select suitable solubilizer, increases solubility of the high condensation point accessory substance in water from reaction gas, makes height
The high condensation point accessory substance that condensation point accessory substance is difficult to separate out or separated out gradually dissolves.With the dissolving of high condensation point accessory substance, prevent
Or reduce the possibility with catalyst fines formation large particulate matter.It can also promote to have formed the high condensation point accessory substance of dirty thing simultaneously
It is dissolved in the water, the online dirty thing removed in water scrubber.Avoid due to the non-normal stop that fouling is caused, be the length of MTO devices
Periodic duty provides necessary condition.
The water scrubber scale remover of the present invention is made, the surfactant for solubilising according to the solubilized principle of solubilizer
Referred to as solubilizer, the process of the solubility formation settled solution of increase indissoluble material is referred to as solubilising.Why solubilizer can increase
The solubility of slightly solubility material, is due to that it can form the result of micelle (micella) in water.Micelle is the oleophylic by solubilizer
Group inwardly (formed a minimum oil droplet, non-polar core area), orbicule formed by hydrophilic radical is outside.Inside whole micelle
It is nonpolar, outside is polarity.Because micelle is small micelle particle.Its dispersion belongs to colloidal solution, so that
Indissoluble material can be made to be contained or adsorbed, increase meltage.The most suitable hydrophilic-hydrophobic balance value (HLB) of solubilizer is 15-18.
The application method of water scrubber scale remover of the present invention is simple, as long as being added in the washing water of water scrubber.Add
As long as concentration is more than critical micelle concentration (CMC).
Compared with prior art, the beneficial effects of the invention are as follows：
(1) the dirty thing generation in water scrubber can effectively be suppressed.
(2) the dirty thing generated in water scrubber can be removed online, it is to avoid due to the non-normal stop that fouling is caused, be
The long-term operation of MTO devices provides necessary condition.
Embodiment
Below by embodiment, the present invention is described further, and raw materials used commercially available in embodiment or use is normal
Rule method is made by oneself, but embodiment is not limit the scope of the invention.
Embodiment 1：
Above-mentioned each component is added separately in container, each component is heated to and is completely dissolved, after being uniformly mixed, cooling
Filtering, is produced a kind of for MTO water scrubbers scale remover 1.
Embodiment 2
Above-mentioned each component is added separately in container, each component is heated to and is completely dissolved, after being uniformly mixed, cooling
Filtering, is produced a kind of for MTO water scrubbers scale remover 2.
Embodiment 3
Above-mentioned each component is added separately in container, each component is heated to and is completely dissolved, after being uniformly mixed, cooling
Filtering, is produced a kind of for MTO water scrubbers scale remover 3.
Embodiment 4
Above-mentioned each component is added separately in container, each component is heated to and is completely dissolved, after being uniformly mixed, cooling
Filtering, is produced a kind of for MTO water scrubbers scale remover 4.
Embodiment 5
Above-mentioned each component is added separately in container, each component is heated to and is completely dissolved, after being uniformly mixed, cooling
Filtering, is produced a kind of for MTO water scrubbers scale remover 5.
Embodiment 6
Above-mentioned each component is added separately in container, each component is heated to and is completely dissolved, after being uniformly mixed, cooling
Filtering, is produced a kind of for MTO water scrubbers scale remover 6.
Embodiment 7
Above-mentioned each component is added separately in container, each component is heated to and is completely dissolved, after being uniformly mixed, cooling
Filtering, is produced a kind of for MTO water scrubbers scale remover 7.
Embodiment 8
Above-mentioned each component is added separately in container, each component is heated to and is completely dissolved, after being uniformly mixed, cooling
Filtering, is produced a kind of for MTO water scrubbers scale remover 8.
Embodiment 9
Above-mentioned each component is added separately in container, each component is heated to and is completely dissolved, after being uniformly mixed, cooling
Filtering, is produced a kind of for MTO water scrubbers scale remover 9.
Embodiment 10
Above-mentioned each component is added separately in container, each component is heated to and is completely dissolved, after being uniformly mixed, cooling
Filtering, is produced a kind of for MTO water scrubbers scale remover 10.
Test case：Water scrubber scale remover scale removal effect assessment
(1) preparation of high condensation point accessory substance
Certain domestic MTO device causes the non-normal stop of whole device due to the fouling and clogging of water scrubber.In water scrubber
The dirty thing of collection in worksite, by processing, has obtained high condensation point accessory substance, gives over to scale remover effect assessment use.
(2) laboratory evaluation
Scale remover in the high condensation point accessory substances of 10g, 0.1g embodiments, 2000g deionized waters are added to stirring dress
In the flask put, be heated to 40 DEG C, suction filtration is removed in stirring insulation 30 minutes, by screening in the case where vacuumizing environment 40 DEG C of constant temperature two
Weighed after hour, obtain weight for W, be not added with scale remover, ibid, obtaining screening weight is for remaining all substances consumption and process step
W0,
Setting：
When being not added with scale remover, the solubility of high condensation point accessory substance is S0
Plus during scale remover, the solubility of high condensation point accessory substance is S
The solubilizing effect of solubilizer is better, means that the scale removal effect of scale remover is better.Now just represented with solubilizing effect D
Scale removal effect.
Solubilizing effect using embodiment 1-10 is as shown in table 1：
Table 1
Claims (2)
1. one kind is used for MTO water scrubber scale removers, it is characterised in that：Following components are put into vessel in heating to molten by scale remover
Solution, stirring mixing is cooled to after room temperature and filters obtained, the parts by weight of each component are：
AEO solubilizer 5-40,
2- nitro -4- APES solubilizer 5-40,
Alkyl phenol polyethenoxy ether sodium sulfate solubilising assistant agent 2-30,
Deionized water 30-60,
Described AEO solubilizer structural formula is such as（I）It is shown：
（I）,
Wherein, R=C12~C18Integer between alkyl, n=15~40；
Described 2- nitro -4- APES solubilizing agent molecules formula is such as（II）It is shown：
（II）,
Wherein, R1=C8~C18Integer between alkyl, m=15~40；
The solubilized assistant agent molecular formula of described alkyl phenol polyethenoxy ether sodium sulfate is such as（III）It is shown：
（III）,
Wherein, R2=C12~C18Integer between alkyl, p=3~4.
2. it is according to claim 1 a kind of for MTO water scrubber scale removers, it is characterised in that：The parts by weight of each component are：
AEO solubilizer 10-30,
2- nitro -4- APES solubilizer 10-30,
Alkyl phenol polyethenoxy ether sodium sulfate solubilising assistant agent 5-20,
Deionized water 30-60.
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| CN201610243528.0A CN105819578B (en) | 2016-04-16 | 2016-04-16 | One kind is used for MTO water scrubber scale removers |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106315756A (en) * | 2016-10-18 | 2017-01-11 | 南昌航空大学 | Device for advanced treatment of organic wastewater through coordination of photocatalysis and fenton oxidation |
| CN110143844B (en) * | 2018-02-12 | 2023-05-26 | 通用电气(Ge)贝克休斯有限责任公司 | Deposit control in methanol to olefins processes |
| CN110713864B (en) * | 2018-07-13 | 2023-09-26 | Bl 科技公司 | Antifouling dispersant compositions and methods of use |
| CN110819470B (en) * | 2019-11-21 | 2021-07-09 | 天津市瑞德赛恩新材料开发有限公司 | Online cleaning agent for olefin separation water washing tower, preparation method and application thereof |
| CN114105323A (en) * | 2020-08-28 | 2022-03-01 | 埃科莱布美国股份有限公司 | Method and extractant for preventing fouling of methanol-to-olefin washing water system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009095147A1 (en) * | 2008-01-30 | 2009-08-06 | Linde Ag | Method for preparing linear alpha-olefins |
| CN101844833A (en) * | 2010-06-13 | 2010-09-29 | 东南大学 | Ultraviolet labelled alkylphenol polyether scale inhibitor and preparation method thereof |
-
2016
- 2016-04-16 CN CN201610243528.0A patent/CN105819578B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009095147A1 (en) * | 2008-01-30 | 2009-08-06 | Linde Ag | Method for preparing linear alpha-olefins |
| CN101844833A (en) * | 2010-06-13 | 2010-09-29 | 东南大学 | Ultraviolet labelled alkylphenol polyether scale inhibitor and preparation method thereof |
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Denomination of invention: A scale remover for MTO water washing tower Effective date of registration: 20230405 Granted publication date: 20170905 Pledgee: Industrial and Commercial Bank of China Limited Deqing sub branch Pledgor: ZHEJIANG HANGHUA TECHNOLOGY CO.,LTD. Registration number: Y2023330000687 |
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| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Granted publication date: 20170905 Pledgee: Industrial and Commercial Bank of China Limited Deqing sub branch Pledgor: ZHEJIANG HANGHUA TECHNOLOGY CO.,LTD. Registration number: Y2023330000687 |