CN110143675A - 工业循环冷却水系统用无磷预膜剂及其制备方法 - Google Patents
工业循环冷却水系统用无磷预膜剂及其制备方法 Download PDFInfo
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- 239000011574 phosphorus Substances 0.000 title claims abstract description 28
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 28
- 239000000498 cooling water Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000003751 zinc Chemical class 0.000 claims abstract description 6
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 10
- 235000011478 zinc gluconate Nutrition 0.000 claims description 9
- 235000018417 cysteine Nutrition 0.000 claims description 8
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 claims description 4
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- 229960000306 zinc gluconate Drugs 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
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- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- NAOLWIGVYRIGTP-UHFFFAOYSA-N 1,3,5-trihydroxyanthracene-9,10-dione Chemical compound C1=CC(O)=C2C(=O)C3=CC(O)=CC(O)=C3C(=O)C2=C1 NAOLWIGVYRIGTP-UHFFFAOYSA-N 0.000 claims 1
- 235000009754 Vitis X bourquina Nutrition 0.000 claims 1
- 235000012333 Vitis X labruscana Nutrition 0.000 claims 1
- 235000014787 Vitis vinifera Nutrition 0.000 claims 1
- 240000006365 Vitis vinifera Species 0.000 claims 1
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
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- 238000012986 modification Methods 0.000 claims 1
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- 239000003814 drug Substances 0.000 abstract description 5
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- 230000005764 inhibitory process Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 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 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
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- -1 gluconic acid radical ion Chemical class 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
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- 230000002195 synergetic effect Effects 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- JHXCINJSAAFBDH-UHFFFAOYSA-N [Ca].O[Si](O)(O)O Chemical compound [Ca].O[Si](O)(O)O JHXCINJSAAFBDH-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
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- 238000000280 densification Methods 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
Classifications
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- 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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/023—Water in cooling circuits
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/11—Turbidity
-
- 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
- C02F2303/08—Corrosion inhibition
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- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
本发明涉及一种工业循环冷却水系统用无磷预膜剂及其制备方法,其特征在于,按重量百分比包括：氨基酸3～5％、改性聚羧酸盐20～40％、锌盐5～15％、浓硫酸1～3％,余量为水。无磷预膜剂各组分协同性好，产品性能稳定，在常温、自然pH、浊度≤20NTU条件下，具有成膜速度快，成膜色泽均匀；另外，本发明的配方原材料是无磷环保的药剂，可以直接排污。
Description
技术领域
本发明涉及一种工业循环冷却水处理技术领域，尤其涉及一种工业循环冷却水系统用无磷预膜剂及其制备方法。
背景技术
清洗预膜是工业循环冷却水处理中一项重要的预处理技术，它是提高系统设备防腐蚀能力的重要手段。预膜剂会在工业循环水系统的金属管线及设备表面形成一层致密耐腐蚀的保护膜，从而起到保护管线与设备，延长其寿命的目的。
工业循环冷却水系统常用的预膜剂有以下几类：1、聚磷酸盐-锌盐；2、有机膦-聚磷酸盐-锌盐；3、钼酸盐-锌盐；4、钨酸盐；5、硅酸盐等。由于钼酸盐、钨酸盐价格昂贵，硅酸盐会带来硅酸钙垢，这样就限制了它们的应用范围。
目前，使用较多的是聚磷酸盐-锌盐预膜剂。它来源广泛，价格低廉，使用范围较广，但其带来的问题也很突出：1、配方中磷含量高，排污时的磷含量远大于污水的标准要求，容易造成水质富营养化，污染环境；2、预膜时条件控制比较严格：如温度、pH、流速等，控制不好会形成难溶的磷酸钙沉淀；3、预膜后需要置换系统中全部的水，造成水资源浪费。
中国专利公开号：CN1754923公开了一种输油管线用预膜剂；包含磷酸盐、硫酸锌，其中所述的磷酸盐可以为聚磷酸钠，聚磷酸钠70％、硫酸锌30％。本发明所述的预膜剂特别适用于输油管线中的管道。本发明的预膜剂能够在管道表面形成致密均匀的膜，并且该膜非常稳定。
由此可见，所述一种输油管线用预膜剂存在以下问题：配方中磷含量高，排污时的磷含量远大于污水的标准要求。
发明内容
为此，本发明提供一种工业循环冷却水系统用无磷预膜剂及其制备方法，用以克服现有技术中配方中磷含量高，排污超标的问题。
为实现上述目的，本发明提供一种一种工业循环冷却水系统用无磷预膜剂，其特征在于,按重量百分比包括：氨基酸3～5％、改性聚羧酸盐20～40％、锌盐5～15％、浓硫酸1～3％,余量为水。进一步地，氨基酸为半胱氨酸，其具有良好
的金属缓蚀性能，来源广泛并在自然环境中可以全部分解，是绿色环保型缓蚀剂；外观：白色结晶粉末，密度： 1.334g/cm3，熔点：220℃，沸点：293.9℃，闪点：131.5℃，溶解度(25℃)： 280g/l。
进一步地，改性聚羧酸盐为丙烯酸-丙烯酸酯-AMPS共聚物，是一种高效阻垢分散剂，对于水中的磷酸钙垢、碳酸钙垢等成垢盐类和无机矿物质具有良好的分散作用，在含锌配方中，也可作为高效率锌盐安定剂；此外，丙烯酸-丙烯酸酯-AMPS共聚物可高效分散所遇到的无机微粒，且可抗拒pH的影响；外观：无色至淡黄色透明液体，固体含量：42～44％，密度(20℃)：≥1.15g/cm3,粘度(20℃)： 100～500cps。
进一步地，锌盐为葡萄糖酸锌，葡萄糖酸根离子本身对金属具有缓蚀作用，它与锌离子有协同效应，因此葡萄糖酸锌是一种缓蚀作用很好的缓蚀剂；葡萄糖酸锌与丙烯酸-丙烯酸羟丙酯-AMPS共聚物有很好的协同效应；外观：白色结晶性或颗粒性粉末，有效物含量：≥97～102％，熔点(℃)：131，沸点(℃)：673.6，闪点(℃)：375.2。
与现有技术相比，本发明的有益效果在于，无磷预膜剂各组分协同性好，产品性能稳定，在常温、自然pH、浊度≤20NTU条件下，具有成膜速度快，成膜色泽均匀；另外，本发明的配方原材料是无磷环保的药剂，可以直接排污。
具体实施方式
为了使本发明的目的和优点更加清楚明白，下面结合实施例对本发明作进一步描述；应当理解，此处所描述的具体实施例仅仅用于解释本发明，并不用于限定本发明。
实施例1
1、将反应釜冲洗干净，关闭放料阀，按重量百分比加入710公斤去离子水，打开搅拌后加入10公斤浓硫酸；
2、然后按重量百分比依次投加200公斤丙烯酸-丙烯酸酯-AMPS共聚物和30 公斤半胱氨酸，最后加入50公斤葡萄糖酸锌，再搅拌45～60分钟，至溶液澄清透明为止；
3、打开放料阀，过滤即得无磷预膜剂产品。实施
例2
1、将反应釜冲洗干净，关闭放料阀，按重量百分比加入370公斤去离子水，打开搅拌后加入30公斤浓硫酸；
2、然后按重量百分比依次投加400公斤丙烯酸-丙烯酸酯-AMPS共聚物和50 公斤半胱氨酸，最后加入150公斤葡萄糖酸锌，再搅拌45～60分钟，至溶液澄清透明为止；
3、打开放料阀，过滤即得无磷预膜剂产品。实施
例3
1、将反应釜冲洗干净，关闭放料阀，按重量百分比加入490公斤去离子水，打开搅拌后加入30公斤浓硫酸；
2、然后按重量百分比依次投加300公斤丙烯酸-丙烯酸酯-AMPS共聚物和30 公斤半胱氨酸，最后加入150公斤葡萄糖酸锌，再搅拌45～60分钟，至溶液澄清透明为止；
3、打开放料阀，过滤即得无磷预膜剂产品。实施
例4
1、将反应釜冲洗干净，关闭放料阀，按重量百分比加入435公斤去离子水，打开搅拌后加入30公斤浓硫酸；
2、然后按重量百分比依次投加375公斤丙烯酸-丙烯酸酯-AMPS共聚物和35 公斤半胱氨酸，最后加入125公斤葡萄糖酸锌，再搅拌45～60分钟，至溶液澄清透明为止；
3、打开放料阀，过滤即得无磷预膜剂产品。实施
例5
1、将反应釜冲洗干净，关闭放料阀，按重量百分比加入490公斤去离子水，打开搅拌后加入30公斤浓硫酸；
2、然后按重量百分比依次投加280公斤丙烯酸-丙烯酸酯-AMPS共聚物和50 公斤半胱氨酸，最后加入150公斤葡萄糖酸锌，再搅拌45～60分钟，至溶液澄清透明为止；
3、打开放料阀，过滤即得无磷预膜剂产品。根据以上实施例，效果评判如下表：
表1实施例效果实验结果
由以上试验数据可以看出，本发明无磷预膜剂在300mg/l的加药浓度下，时间差大的达到44s，最小的达到30s，在500mg/l的加药浓度下，时间差大的达到77s，最小的达到55s，现场药剂在300mg/l的加药浓度下，时间差为7s，在 500mg/l的加药浓度下，时间差为30s，这些数据可以说明本发明的无磷预膜剂的成膜性能要优于现场药剂，并且成膜色泽均匀。说明本发明的无磷预膜剂各组分协同性好，产品性能稳定，在常温、自然pH、浊度≤20NTU条件下，具有成膜速度快，成膜色泽均匀；另外，本发明的配方原材料是无磷环保的药剂，可以直接排污，能够满足循环水系统的实际生产需求。
至此，已经结合优选实施方式描述了本发明的技术方案，但是，本领域技术人员容易理解的是，本发明的保护范围显然不局限于这些具体实施方式。在不偏离本发明的原理的前提下，本领域技术人员可以对相关技术特征做出等同的更改或替换，这些更改或替换之后的技术方案都将落入本发明的保护范围之内。
Claims (6)
1.一种工业循环冷却水系统用无磷预膜剂，其特征在于,按重量百分比包括：氨基酸3～5％、改性聚羧酸盐20～40％、锌盐5～15％、浓硫酸1～3％,余量为水。
2.根据权利要求1所述工业循环冷却水系统用无磷预膜剂，其特征在于,所述氨基酸为半胱氨酸。
3.根据权利要求1所述工业循环冷却水系统用无磷预膜剂，其特征在于,所述改性聚羧酸盐为丙烯酸-丙烯酸酯-AMPS共聚物。
4.根据权利要求1所述工业循环冷却水系统用无磷预膜剂，其特征在于,所述锌盐为葡萄糖酸锌。
5.根据权利要求1所述工业循环冷却水系统用无磷预膜剂，其特征在于,所述水为去离子水。
6.一种工业循环冷却水系统用无磷预膜剂的制备方法，其特征在于，所述制备方法包括以下步骤：
第一步，将反应釜冲洗干净，关闭放料阀，加入去离子水，搅拌过程中加入浓硫酸；
第二步，依次投加丙烯酸-丙烯酸酯-AMPS共聚物和半胱氨酸，最后加入葡萄糖酸锌，再搅拌45～60分钟，至溶液澄清透明为止；
第三步，打开放料阀，过滤即得无磷预膜剂产品。
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Denomination of invention: Phosphorus free pre film agent and its preparation method for industrial circulating cooling water system Granted publication date: 20211119 Pledgee: Beijing Bank Co.,Ltd. Urumqi Branch Pledgor: DELAND WATER TECHNOLOGY CO.,LTD. Registration number: Y2024650000002 |