CN113881517A - Heat exchanger scale cleaning agent, preparation method and use method - Google Patents
Heat exchanger scale cleaning agent, preparation method and use method Download PDFInfo
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- CN113881517A CN113881517A CN202111170268.6A CN202111170268A CN113881517A CN 113881517 A CN113881517 A CN 113881517A CN 202111170268 A CN202111170268 A CN 202111170268A CN 113881517 A CN113881517 A CN 113881517A
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- heat exchanger
- cleaning agent
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- 239000012459 cleaning agent Substances 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 80
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 18
- 230000007935 neutral effect Effects 0.000 claims abstract description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 7
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims abstract description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 6
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 6
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 6
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 6
- 229940023144 sodium glycolate Drugs 0.000 claims abstract description 6
- JEJAMASKDTUEBZ-UHFFFAOYSA-N tris(1,1,3-tribromo-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CBr)OC(Br)(Br)C(C)(C)CBr JEJAMASKDTUEBZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229960001484 edetic acid Drugs 0.000 claims description 24
- 238000004140 cleaning Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910001424 calcium ion Inorganic materials 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 3
- 239000002671 adjuvant Substances 0.000 claims description 3
- 239000010962 carbon steel Substances 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 229910001200 Ferrotitanium Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 238000005260 corrosion Methods 0.000 abstract description 16
- 230000007797 corrosion Effects 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 5
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 29
- 238000004090 dissolution Methods 0.000 description 13
- 239000012530 fluid Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 238000012546 transfer Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 206010067482 No adverse event Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- -1 calcium sulfate form calcium salt Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3245—Aminoacids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/12—Carbonates bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/261—Alcohols; Phenols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/20—Industrial or commercial equipment, e.g. reactors, tubes or engines
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
The invention discloses a heat exchanger scaling cleaning agent, a preparation method and a use method, the heat exchanger cleaning agent provided by the invention is a special cleaning agent for calcium sulfate, and mainly comprises a base agent, an auxiliary agent and a pH regulator, wherein the base agent comprises one or more of EDTA, EDTA-2Na, EDTA-4Na and sodium glycolate, the auxiliary agent comprises one or more of sodium carbonate, potassium carbonate, ammonium bicarbonate and ammonium citrate, the pH regulator comprises one or more of hydrochloric acid, sulfamic acid and carbonic acid, the mass ratio of the base agent to the auxiliary agent is 1: 1-5: 1, and the pH of the heat exchanger scaling cleaning agent is 6.5-7.5. The cleaning agent is neutral, has no toxic and harmful components, is low in cost, can be prepared at normal temperature, and has no corrosion to equipment materials. And the process of removing calcium sulfate by the cleaning agent does not need high-temperature reaction. Is a special neutral cleaning agent for dissolving calcium sulfate with excellent composition and use performance.
Description
Technical Field
The invention relates to the technical field of heat exchanger scale cleaning agents, and particularly relates to a heat exchanger scale cleaning agent, a preparation method and a use method.
Background
The heat exchanger is the most widely used cold heat exchanger in oil refineries and chemical plants, the heat transfer efficiency is low due to the scaling problem of the heat exchanger, and the heat exchanger needs to be stopped for cleaning or replaced integrally. The heat exchanger problem caused by scaling is treated every year, so that the operation cost is greatly increased, and the safe and stable operation of the device is seriously influenced.
The cleaning method for heat exchanger scaling at present generally adopts a chemical cleaning technology, and the heat exchanger is soaked in high-temperature alkali liquor and then is subjected to acid cleaning treatment. The method is complicated, the cleaning treatment time is long, the energy is consumed, and the heat exchanger tube bundles of the refinery and the chemical plant are mostly made of stainless steel and titanium materials, and the stainless steel and the titanium materials are seriously corroded by high-temperature alkali liquor and acid liquor, so that the washing liquor on the market is not suitable for the heat exchanger descaling. The research on the chemical cleaning agent for effectively removing the heat exchanger scale has very important practical significance.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a heat exchanger scale cleaning agent, a preparation method and a use method.
The invention is realized by the following steps:
the invention provides a heat exchanger scaling cleaning agent which is a special neutral cleaning agent for calcium sulfate, and mainly comprises a base agent, an auxiliary agent and a pH regulator, wherein the base agent comprises at least one of EDTA (ethylene diamine tetraacetic acid), sodium salt of EDTA and sodium glycol glycolate, the auxiliary agent comprises at least one of carbonate and citrate, and the mass ratio of the base agent to the auxiliary agent is 1: 1-5: 1.
The invention also provides a preparation method of the heat exchanger scale cleaning agent, which comprises the following steps: and uniformly mixing the base agent, the auxiliary agent and water, and then adding a pH regulator to regulate the pH of the solution to be neutral, thereby obtaining the heat exchanger scaling cleaning agent.
The invention also provides a use method of the heat exchanger scale cleaning agent, which comprises the following steps: and adding the heat exchanger scaling cleaning agent into the heat exchanger to clean the scaled heat exchanger.
The invention has the following beneficial effects:
the invention provides a heat exchanger scaling cleaning agent, a preparation method and a use method, the provided heat exchanger cleaning agent is a special neutral cleaning agent for calcium sulfate, the cleaning agent mainly comprises a base agent, an auxiliary agent and a pH regulator, the base agent comprises at least one of EDTA (ethylene diamine tetraacetic acid), sodium salt of EDTA and sodium glycol glycolate, the auxiliary agent comprises at least one of carbonate and citrate, and the mass ratio of the base agent to the auxiliary agent is 1: 1-5: 1. The base agent and the calcium sulfate form calcium salt through chelation, the product has good solubility, the auxiliary agent is helpful for exciting chelation reaction, and the dissolution and the stability of the dissolution product are improved so as to be dissolved and removed. The pH regulator regulates the pH of the cleaning agent to be neutral, and prevents the cleaning agent from corroding the heat exchanger base material. The provided heat exchanger cleaning agent is a special neutral cleaning agent which can dissolve calcium sulfate at a non-high temperature by a one-step method. The cleaning agent is a calcium sulfate dissolved heat exchanger scaling cleaning agent with excellent composition and service performance.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The heat exchanger scaling costs a lot every year, and in severe cases, the safety production is affected. Fouling of a heat exchanger refers to the gradual build-up of solid material on the surface of a solid in which the heat exchanger is in contact with unclean fluid. The influence of scaling on heat exchange equipment mainly comprises: the dirt layer has very low heat conductivity coefficient, so that heat transfer resistance is increased, and heat transfer efficiency of heat exchange equipment is reduced; when the surface of the heat exchange equipment is formed with the scale formation, the flow area of a fluid channel in the heat exchange equipment is reduced, so that the resistance of the fluid flowing through the equipment is increased, more pump power is consumed, and the production cost is increased.
According to the mechanism of deposition of the fouling layer, fouling can be classified into particulate fouling, crystalline fouling, chemically reactive fouling, corrosive fouling, biological fouling, and the like.
1. Particle fouling: accumulation of solid particles suspended in a fluid on heat exchange surfaces. Such fouling also includes the deposition of a layer of larger solid particles on the horizontal heat exchange surfaces by gravity, so-called precipitated fouling and other colloidal particles.
2. Crystalline fouling: the inorganic salts dissolved in the fluid crystallize on the heat exchange surfaces to form deposits, which usually occur upon over-saturation or cooling. Typical fouling is the cooling water side of calcium carbonate, calcium sulfate and silica scale layer.
3. Fouling by chemical reaction: fouling resulting from chemical reactions occurring on the heat transfer surface, the heat transfer surface material does not participate in the reaction, but can act as a catalyst for the chemical reaction.
4. Corrosion and fouling: the fluid is corrosive or contains corrosive impurities to corrode the heat exchange surface to produce fouling. Generally, the degree of corrosion depends on the composition of the fluid, the temperature, and the pH of the fluid being treated.
5. Biofouling: with the exception of seawater cooling devices, biofouling is generally referred to as microbial fouling. It may produce slime which in turn provides conditions for the propagation of biofouling, which is very temperature sensitive and which under moderate temperature conditions can produce a fouling layer of considerable thickness.
6. Solidification of dirt: fouling due to solidification of fluid on the super cooled heat exchange surface. For example, when water is below freezing point and freezes to ice on the heat exchange surfaces. Whether the temperature distribution is uniform or not greatly affects such fouling.
As can be seen from the above, there are various causes for the heat exchanger fouling, and long-term observation and practice of the inventor find that crystalline fouling, which forms deposits by crystallization of inorganic salts on the heat exchanger surfaces, is one of the important causes for the heat exchanger fouling, and among them, calcium sulfate is the most common and large in amount and the most difficult to remove.
In order to remove calcium sulfate crystals in heat exchanger scaling quickly and effectively without equipment corrosion and with low cleaning energy consumption, the invention provides a special neutral cleaning agent for calcium sulfate, which mainly comprises a base agent, an auxiliary agent and a pH regulator, wherein the base agent comprises at least one of EDTA (ethylene diamine tetraacetic acid), sodium salt of EDTA and sodium glycol glycolate, the auxiliary agent comprises at least one of carbonate and citrate, the mass ratio of the base agent to the auxiliary agent is 1: 1-5: 1, and the pH value of the heat exchanger scaling cleaning agent is 6.5-7.5. The cleaning agent is a special neutral cleaning agent which can dissolve calcium sulfate at a non-high temperature by a one-step method. The cleaning agent does not need high-temperature reaction, most of calcium sulfate in scaling can be cleaned and removed at normal temperature, and the cleaning agent has no corrosivity on heat exchanger equipment.
In order to achieve the above object of the present invention, the following technical solutions are adopted:
in a first aspect, the embodiment of the invention provides a heat exchanger scaling cleaning agent, which is a special neutral cleaning agent for calcium sulfate, and mainly comprises a base agent, an auxiliary agent and a pH regulator, wherein the base agent comprises at least one of EDTA (ethylene diamine tetraacetic acid), a sodium salt of EDTA and sodium glycolate, the auxiliary agent comprises at least one of carbonate and citrate, and the mass ratio of the base agent to the auxiliary agent is 1: 1-5: 1. The scale sample cannot be dissolved due to too low proportion of the cleaning agent, and the reagent is wasted due to too high proportion of the cleaning agent.
The embodiment of the invention provides a heat exchanger scaling cleaning agent, which is a special neutral cleaning agent for calcium sulfate, and because the main substance in heat exchanger scaling is calcium sulfate, but the calcium sulfate is insoluble in water, ethanol and most organic solvents, the difficulty in removing the calcium sulfate scale is greatly increased, the existing methods of conversion descaling, direct dissolution descaling and the like still have the outstanding problems of complex operation, equipment corrosion, high cleaning energy consumption and the like. And the addition of the auxiliary agent can accelerate the reaction speed of EDTA and calcium sulfate, and the pH value of the cleaning agent is controlled to be close to neutral, so that on one hand, stable calcium salt can be generated, and more importantly, the cleaning agent basically cannot corrode equipment under the neutral condition, and compared with the existing method for soaking and descaling under the acid-base condition, the corrosion effect of cleaning on the equipment is greatly reduced.
In an alternative embodiment, the base comprises at least one of EDTA, EDTA-2Na, EDTA-4Na, and sodium glycolate.
In an alternative embodiment, the adjuvant comprises at least one of sodium carbonate, potassium carbonate, ammonium bicarbonate and ammonium citrate.
In an alternative embodiment, the pH adjusting agent comprises at least one of hydrochloric acid, sulfamic acid and carbonic acid.
In an optional embodiment, the pH value of the heat exchanger fouling cleaning agent is 6.5-7.5.
In a second aspect, an embodiment of the present invention further provides a preparation method of the above cleaning agent for fouling of a heat exchanger, which includes: and uniformly mixing the base agent, the auxiliary agent and water, and then adding a pH regulator to regulate the pH of the solution to obtain the heat exchanger scaling cleaning agent.
In an alternative embodiment, the preparation of the heat exchanger fouling cleaning agent is carried out at ambient temperature.
In an alternative embodiment, the method comprises the following steps: at normal temperature, mixing a base agent and an auxiliary agent according to a mass ratio of 1: 1-5: 1, then mixing the mixture with deionized water to obtain a uniform mixed solution, adding a pH regulator to adjust the pH of the mixed solution to 6.5-7.5 to obtain a colorless clear liquid, namely the heat exchanger scaling cleaning agent.
In a third aspect, an embodiment of the present invention further provides a method for using the above cleaning agent for fouling of a heat exchanger, which includes: and adding the heat exchanger scaling cleaning agent into the scaled heat exchanger to clean the heat exchanger.
In an optional embodiment, during cleaning, a scale sample of the heat exchanger, which is scaled, is taken firstly, the content of calcium ions in the scale sample is analyzed, and the dosage of the heat exchanger cleaning agent is determined according to the content of the calcium ions in the scale sample.
In an optional embodiment, the molar ratio of the heat exchanger fouling cleaning agent to calcium ions in the heat exchanger fouling is 5: 1-1: 1.
In an alternative embodiment, the washing is performed at 50-70 ℃.
In an alternative embodiment, the heat exchanger tube bundle is made of any one of stainless steel, titanium and carbon steel.
The preparation and use conditions of the heat exchanger descaling cleaning agent provided by the embodiment of the invention are mild, the preparation can be carried out at normal temperature, the cleaning agent is used at 50-70 ℃, and compared with the cleaning operations such as high temperature and stewing, the cleaning condition provided by the embodiment of the invention can greatly reduce the cleaning energy consumption, and the cleaning agent has the advantages of simple use process and high descaling efficiency.
Therefore, the embodiment of the invention provides a heat exchanger scaling cleaning agent, a preparation method and a use method. The base agent comprises one or more of EDTA, EDTA-2Na, EDTA-4Na and sodium glycolate, the auxiliary agent comprises one or more of sodium carbonate, potassium carbonate, ammonium bicarbonate and ammonium citrate, and the pH regulator comprises one or more of hydrochloric acid, sulfamic acid and carbonic acid.
Preparation of the cleaning agent: the cleaning agent is prepared by uniformly mixing a base agent and an auxiliary agent according to the proportion of 1: 1-5: 1 with deionized water at the temperature of 25 ℃, and adding a pH regulator to regulate the pH of the solution to 6.5-7.5. The cleaning agent is colorless clear liquid after being prepared, is easy to store and transport and has no corrosiveness.
The method for cleaning scale by using the cleaning agent comprises the following steps: when the cleaning agent is used for cleaning calcium sulfate scale, the molar ratio of the cleaning agent to calcium ions is 5: 1-1: 1, and the cleaning is carried out at the temperature of 50-70 ℃.
The features and properties of the present invention are described in further detail below with reference to examples.
In the following examples of the present invention, the raw material sources, components, preparation and experimental methods were the same as those of the comparative examples.
Example 1
The heat exchanger cleaning agent is prepared as follows: mixing 3 parts of EDTA-2Na and 1 part of sodium carbonate, uniformly mixing with 30 parts of deionized water at the temperature of 25 ℃, and adding sulfamic acid to adjust the pH of the solution to 6.5. The obtained colorless clear liquid is the descaling cleaning agent for the heat exchanger.
Example 2
The heat exchanger cleaning agent is prepared as follows: 5 parts of EDTA-4Na and 2 parts of potassium carbonate are mixed, and the mixture is uniformly mixed with 50 parts of deionized water at the temperature of 25 ℃, and hydrochloric acid is added to adjust the pH value of the solution to 6.5. The obtained colorless clear liquid is the descaling cleaning agent for the heat exchanger.
Example 3
The heat exchanger cleaning agent is prepared as follows: 3 parts of EDTA and 3 parts of sodium carbonate are mixed, and the mixture is uniformly mixed with 40 parts of deionized water at the temperature of 25 ℃, and hydrochloric acid is added to adjust the pH value of the solution to 6.8. The obtained colorless clear liquid is the descaling cleaning agent for the heat exchanger.
Example 4
Aiming at serious blockage of a circulating cooling water heat exchanger tube bundle of a certain chemical device, field scale sample analysis is carried out, 99% of the circulating cooling water heat exchanger tube bundle is calcium sulfate precipitate, the heat exchanger tube bundle is made of industrial pure titanium, TA2, and a shell is made of 304L. The cleaning agent prepared in the patent is used for cleaning calcium sulfate scale samples, and a 304L test piece and a TA2 test piece are added to test whether the cleaning agent corrodes two materials or not.
The test conditions are as follows: the cleaning agent prepared by the method of the invention; scale sample preparation: calcium sulfate scale samples taken out of the on-site heat exchanger; temperature: at 60 ℃. The test procedure was as follows:
1. preparing 1L of cleaning agent;
2. taking 20g of scale sample, directly putting the scale sample into a three-neck flask without crushing;
3. polishing 304L and TA2 test pieces, cleaning, drying, weighing, and respectively putting into two three-neck flasks with the same mass of scale samples;
4. adding the same mass of cleaning agent into the two three-neck flasks, wherein the mass of the cleaning agent is calculated according to the molar ratio of the cleaning agent to the calcium ions;
5. respectively fixing the two three-mouth flasks in an electric heating sleeve, setting the temperature to be 60 ℃, opening a magnetic rotor, and heating and stirring;
6. after reacting for 12 hours, taking out the test piece, washing and weighing;
7. pouring the reacted solution into a Buchner funnel, carrying out vacuum filtration, drying the residual solid and weighing;
and (3) test results: a small amount of calcium sulfate solid remained in both flasks, the remaining dissolution rate is shown in Table 1, the surfaces of 304L and TA2 have no obvious corrosion morphology, and the corrosion rate is shown in Table 2.
TABLE 1 dissolution rate of calcium sulfate solids
| Numbering | Original solid mass (g) | Mass of remaining solid (g) | Dissolution rate (%) |
| Flask 1 | 20.00 | 2.30 | 88.5 |
| Flask 2 | 20.00 | 2.16 | 89.2 |
TABLE 2 Corrosion rates of two materials
| Material of | Weight before reaction (g) | Weight after reaction (g) | Corrosion Rate (mm/a) |
| 304L | 7.81783 | 7.81016 | 0.0022 |
| TA2 | 4.52538 | 4.52519 | 0.0001 |
From the above tables 1 and 2, it can be seen that the descaling cleaning agent for heat exchangers provided in the embodiment 1 of the present invention can dissolve calcium sulfate solids well, the dissolution rate is close to 90%, and meanwhile, the corrosion effect of 304L and TA2 added in the cleaning process is very small, and the corrosion rate is very low.
Application example
When the titanium heat exchanger is used specifically, when a certain refinery is overhauled, the inside of the titanium heat exchanger is seriously blocked, a scale sample is taken for analysis, and the main component is CaSO4The cleaning agent disclosed by the invention is added, the heat exchanger is sealed, the heat exchanger is soaked for 48 hours at the temperature of 60 ℃, the heat exchanger is opened, flowing clear water is used for cleaning the interior of the heat exchanger, more than 90% of scale samples are completely removed, and no obvious corrosion trace exists on the surface of the titanium heat exchanger.
Comparative example 1
Different from the composition of the cleaning agent of the invention. The composition of the cleaning agent is hydrochloric acid and ammonium bicarbonate, and the result is that: because the cleaning agent does not contain a base agent, calcium ions in the calcium sulfate cannot be complexed, and the calcium sulfate can be dissolved, but the hydrochloric acid which needs to be used has high concentration and large usage amount, so that the material of the device is corroded.
Comparative example 2
Similar to the procedure of example 1, except that: the auxiliary agent component in the cleaning agent is replaced by sodium sulfate, and the result is that: after the same soaking time, the dissolution rate of calcium sulfate was greatly reduced to only 67% (due to the reduced reaction rate, the dissolution rate of calcium sulfate was reduced in the same time).
Comparative example 3
Similar to the procedure of example 1, except that: the absence of a pH modifier in the cleaner resulted in: the pH of the cleaner was more basic and the corrosion rates of carbon steel, stainless steel and TA2 were all increased over those of example 5.
Comparative example 4
Similar to the procedure of example 1, except that: the ratio of base agent to adjuvant was 10:1, the result was: after the soaking for the same time, the dissolution rate of the calcium sulfate is greatly reduced to 73.2 percent.
Comparative example 5
Similar to the procedure of example 1, except that: the ratio of the base agent to the auxiliary agent is 1:10, and the result is that: after the soaking for the same time, the dissolution rate of the calcium sulfate is greatly reduced to only 23.7 percent.
The auxiliary agent is replaced by sodium sulfate, or the proportion of the base agent and the auxiliary agent is changed, so that the dissolution rate of calcium sulfate is reduced, and the complex reaction cannot be effectively accelerated.
The addition of carbonate increases the reaction kinetics of EDTA to calcium sulfate sequestration. The greater reaction kinetics are due to the greater solubility equilibrium of the reaction products. Taking sodium carbonate as an example:
2CaSO4+2Na3HEDTA+Na2CO3＝2CaNaEDTA+2Na2SO4+H2CO3
the generation of carbonic acid by the reaction, released from the solution, will effectively promote the reaction to move to the right, i.e. promote the dissolution of calcium sulfate by EDTA/EDTA sodium salt. The addition of carbonate does not increase the dissolving power of EDTA, but increases the reaction speed.
Compared with the cleaning agent in the prior art, the descaling cleaning agent for the heat exchanger provided by the embodiment of the invention has the following advantages:
firstly, the cleaning agent is neutral and has no corrosion to equipment materials.
Secondly, the cleaning agent disclosed by the invention is simple in preparation process, nontoxic in components and low in price, and can be prepared at normal temperature.
Thirdly, the process of removing calcium sulfate by the cleaning agent does not need high-temperature reaction.
The heat exchanger scale cleaning agent processed by the embodiment of the invention mainly comprises a base agent, an auxiliary agent and a pH regulator, wherein the pH value is 6.5-7.5, when the cleaning agent is used for removing sulfate insoluble salt scale, the cleaning agent can completely remove hard scale, cannot corrode enamel, glass and the like, and has no adverse reaction to human body contact, the cleaned waste liquid can be directly discharged into a wastewater treatment system, the use function of the cleaned heat exchanger element is completely the same as that of a new element, the stable operation time of equipment is greatly prolonged, and the benefit is obvious; the heat exchanger scaling cleaning agent provided by the embodiment of the invention only needs normal-temperature cleaning without steam catalysis; the cleaning cycle of the invention is short (1 day); the cleaning efficiency is high, and the descaling rate is more than 85%.
In summary, the cleaning agent provided by the embodiment of the invention is a special cleaning agent for calcium sulfate, and mainly comprises a base agent, an auxiliary agent and a pH regulator, wherein the base agent comprises one or more of EDTA, EDTA-2Na, EDTA-4Na and sodium glycolate, the auxiliary agent comprises one or more of sodium carbonate, potassium carbonate, ammonium bicarbonate and ammonium citrate, the pH regulator comprises one or more of hydrochloric acid, sulfamic acid and carbonic acid, the mass ratio of the base agent to the auxiliary agent is 1: 1-5: 1, and the pH of the cleaning agent for heat exchanger scaling is 6.5-7.5. The cleaning agent provided by the embodiment of the invention is neutral and has no corrosion to equipment materials. The cleaning agent has simple preparation process, no toxic or side effect on components and low cost, and can be prepared at normal temperature. And the process of removing calcium sulfate by the cleaning agent does not need high-temperature reaction. Is a special neutral cleaning agent for dissolving calcium sulfate with excellent composition and practical performance.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The heat exchanger scaling cleaning agent is characterized by being a special neutral cleaning agent for calcium sulfate, and mainly comprising a base agent, an auxiliary agent and a pH regulator, wherein the base agent comprises at least one of EDTA (ethylene diamine tetraacetic acid), sodium salt of EDTA and sodium glycol glycolate, the auxiliary agent comprises at least one of carbonate and citrate, and the mass ratio of the base agent to the auxiliary agent is 1: 1-5: 1.
2. The heat exchanger scale cleaning agent according to claim 1, wherein the base agent comprises at least one of EDTA, EDTA-2Na, EDTA-4Na, and sodium glycolate.
3. The heat exchanger fouling cleaning agent of claim 1, wherein the adjuvant comprises at least one of sodium carbonate, potassium carbonate, ammonium bicarbonate and ammonium citrate.
4. The heat exchanger fouling cleaning agent of claim 1, wherein the pH adjusting agent comprises at least one of hydrochloric acid, sulfamic acid and carbonic acid.
5. The heat exchanger fouling cleaning agent according to any one of claims 1 to 4, wherein the pH of the heat exchanger fouling cleaning agent is 6.5 to 7.5.
6. A method for preparing a heat exchanger fouling cleaning agent according to any one of claims 1-5, characterized in that the method comprises the following steps: and uniformly mixing the base agent, the auxiliary agent and water, and then adding a pH regulator to regulate the pH of the solution to be neutral, thereby obtaining the heat exchanger scaling cleaning agent.
7. The method of claim 6, comprising the steps of: at normal temperature, mixing a base agent and an auxiliary agent according to a mass ratio of 1: 1-5: 1, then mixing the mixture with deionized water to obtain a uniform mixed solution, adding a pH regulator to adjust the pH of the mixed solution to 6.5-7.5 to obtain a colorless clear liquid, namely the heat exchanger scaling cleaning agent.
8. A method for using the heat exchanger fouling cleaning agent according to any one of claims 1 to 5 or the heat exchanger fouling cleaning agent prepared by the preparation method according to any one of claims 6 to 7, characterized by comprising: and adding the heat exchanger scaling cleaning agent into the scaled heat exchanger to clean the scale of the heat exchanger.
9. The use method of claim 8, wherein during cleaning, a scale sample of the heat exchanger scale is taken firstly, the content of calcium ions in the scale sample is analyzed, and the dosage of the heat exchanger cleaning agent is determined according to the content of the calcium ions in the scale sample;
preferably, the washing is carried out at a temperature of 50-70 ℃,
preferably, the molar ratio of the heat exchanger fouling cleaning agent to calcium ions in the heat exchanger fouling is 5: 1-1: 1.
10. The use method according to claim 8, wherein the heat exchanger tube bundle is made of any one of stainless steel, titanium and carbon steel.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115449440A (en) * | 2022-08-24 | 2022-12-09 | 翱途能源科技(无锡)有限公司 | Cleaning agent and preparation process thereof |
| CN115960681A (en) * | 2022-12-22 | 2023-04-14 | 江苏三美化工有限公司 | Cleaning agent for hydrogen fluoride rectification system and sensor thereof |
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| US20190071597A1 (en) * | 2017-09-01 | 2019-03-07 | Fluid Energy Group Ltd. | Composition useful in sulfate scale removal |
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| US4144185A (en) * | 1978-02-24 | 1979-03-13 | The United States Of America As Represented By The Secretary Of The Interior | Method and composition for removing calcium sulfate scale deposits from surfaces |
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