CA1087480A

CA1087480A - Gas scrubber scale and deposit control

Info

Publication number: CA1087480A
Application number: CA269,079A
Authority: CA
Inventors: Gerald E. Welder; Edward R. Lang; Charles W. Slagle
Original assignee: Calgon Corp
Current assignee: Calgon Corp
Priority date: 1976-01-07
Filing date: 1977-01-04
Publication date: 1980-10-14
Also published as: NO144619B; IE44558B1; BR7608838A; DK153367B; LU76525A1; DE2700347A1; NO764352L; FR2337694B1; NL7614213A; GB1532391A; DE2700347C2; FI763638A; IE44558L; SE7614102L; NO144619C; CH624368A5; SE435456B; NL185221B; JPS52110288A; IT1121700B

Abstract

A B S T R A C T

Use of a high molecular weight polymer and a scale inhibitor to control deposit build-up in gas scrubbers.

Description

~37~

BA CK GROUND OF T~E IN VENTIOl~l During recent years, the number of wet scrubber systems installed to remove gaseous and particulate material from waste stack gases has increased tremendously. Additional such systems are on the drawing board now. These wet scrubbers are being used to clear effluent from boiler stacks, incinerator stacks~ lime kilns, foundries, blast furnaces, basic oxygen furnaces (BOF), open hearth unitsJ coke plants, paper mill recovery boilers, pet food manufacturing facilities, electric furnaces (steel and aluminum), smelters~, asphalt plants and many others.

One of the most important features of a scrubber system is the COntaCt cha~lber~, the device used to eFfect transfer of gaseous and/or i~
particulate matter from the gas to the water phase. Most wet scrubber systems involve a venturi, a packed bed, an orifice plate, ~L spray chamber or a turbulent bed. Some systems even use two contact chambers in series, for example, a venturi followed by a spray

2 0 chamber .

. ` .
Venturi or orifice plate scrubbers are generally more efficient for particulate removal while paclced beds, turbulent beds and spray chambers are usually Inore efficient for removing gaseous components such as SO2 and HF.

L~
.- .

.'' ''.
i~ , , . , . - ., ...... . . ~ . , . . . . :

C..1154IA
~8~4~3~

The present invention is directed specifically to those scrubber systems where scaling and deposition problems due to insoluble calcium carbonate, calcium fluoride~, iron o~ide (Fe203)~ silica, manganese oxide~ iron ore fines and slag fines are encountered~ The type problem S which the present invention mi~limizes is that which is found in gas scrubber systems of blast furnace operations where iron ore is being converted or processed to iron having a high carbon content.

In order to assure a complete understanding of the problem to which the present invention is addressed, a brief description of a blast furnace operation is hereafter provided.

In the production of iron, iron ore is fed together with additional ingredients such as dolomite through the top of a blast furnace fired by coke. An air stream is blown upward frorn the bottom of the furnace through the subsequent molten materials~ The carbon of the coke reduces the iron ore (FezO3) to iron metal. The molten iron is tapped from the bottom of the furnace while the slag is tapped from the middle of the furnace. The by..product of the carbon reduction is of course a combination of carbon dioxide and carbon monoxide which reacts with the calcium present to form the troublesome scaleformerA calcium ZO carbonate and other solids: clay, slag, fines, etc.
. ~' .
As can be appreciated~ the air stream blown upward contributes significantly to the impurity content of the flue gas, thus putting an extreme burden on the scrubbing system. The particulate load in the ~ -scrubbing ~nediun~ ranges from about 1, 000 to 2, 000 parts per million 2S because of the particulate load of the flue gas. ~`
-''.

_ 2 - ~

9 ~79L~ C- 1 1 54IA

The scrubbers that are used in blast furnace gas clean~up are often of the Venturi design and treat the off~gases from the furnace.
These gases contain significant quantities of iron oxide~ whose fine particle si~7e allows it to be carried of~ in the gas stream. Also present may be coke fines, to a lesser extent and to some extent, particulate slag materials used, such as silicates and unused dolomitesO
The iron oxide has been subjected to high temperatures within the furnace and may therefore be in a sintered form of low surface activity.
Ho~vever, its fine particle size presents deposition problems in scrub~
bers and delivery lines.

Another example of an operative system is a basic oxygen furnace (BOF) in which the BOF receives molten metal from the blast furnace plus scrap, various alloys to meet specifications, and lime and fluorspar as a flux. Oxygen is introduced through a lance to remove impurities. The oxygen blow can release 4. 4 tons of dust per 220 ton heat. This dust must be removed fro~ the waste gas. The dust con sists o iron o~ide, lime and fluoride.

This particulate and soluble gases are removed from the waste gas in a wet scrubber. In the scrubber water the iron oxide, calcium fluoride and calcium carbonate combine to cause massive deposit build-up on the scrubber system intervals which result in inefficient scrubber operation and high maintenance costs. ~ -Prior art methods, such as the method set forth in U. S. Patent No. 3~ 880, 620, employ scale inhibitorsJ i. e., inorganic and organic phosphates; and low molecular weight polymeric dispersants This ',. ' . ' '

3 _ `'' .

~ ~ ~ `

4~ C~ 1 1 54IA

approach has not been completely successful in preventing deposition and has resulted in increased treatment costs and frequent shutdowns for mechanical cleaning.

~ccordingly, it is an ob~ect of this invention to provide a composition and method of effectively preventing deposits in gas s crubber s .

It is a further object of th;s invention to provide a composition and method for preventing deposits in gas scrubbers which is economical and which minimizes the frequency of ~nechanically cleaning scrubber 1 0 equipment.

It is still a further object of this invention to provide a compo-sition and method of preventing deposits in gas scrubbers which is effective over a wide range of pH conditions, These and other objects of this invention are accomplished by 1~ the composition and method of this invention in which from about 0. 01 to about 100 ppm active ingredients, preferably from about .1 to about 10 ppm active ingredients, of a composition comprising a scale :
inhibitor and a high molecular weight polymer is maintained in the :
aqueous scrubbing medium. The ratio of scale inhibitor to high molecular weight polymer may be from about 1:10 to about 10 preferably from about 1:5 to about 5:1~ by weight.
' Suitable threshold scale inhibitors include phosphonates of the general formula:

, ~ ' ~ ' '' _ 4 ~.
, :~ - . . . . :, . . ... . .

C~115a~IA

R\ _ _ N ~ (CH2CH2)X ~ N- _ R
R/ ~ R_ n :
wherein. R is ... ..... .
O
_ CH2 -- P ~ OM
OM
is H, NH~L, alkali metal or combinations thereof;
n i6 0 to 6; and x is 1 to 6; and those of the general formula:
O R C) " I Ir HO _ P ~ C _ P ~ OH
t OH X OH
wherein X is c~ OH or ~ NH2 and R is an alkyl group of frorn 1 to 5 . ~ .., 15 carbon atoms. The most preferred cornpounds, however~, are amino ;
tris ~methylene phosphonic acid) and hydroxyethylidene-lg l-.diphos.~ ... .:phonic acid (HEDP) and water~soluble salts thereof.
' Also useful as threshold scale inhibitors are phosphates such .
as polyphosphates, as for example sodium polyphosphates and phos-Z0 phate esters of the formula:

., N ~ RDPO3M2 ] 3 :',',', ""~, whexein M may be .. H, r. NH2 or a monovalent metal ion and 1~ is an . ~: . -alkylene group having from 1 to 18 carbon atoms. Suitable polyphos- `
phates are disclosed in U. S. Patent Nos. 2, 337, 856, 2, 906, 599 and .:
3~ 213, 017. .~ . . ' , ~ 5 ..
,. .

'. .: " ' '.' ;, . ' : ~ : ' , ',` .' '.. '; " ' ' -.

7~B~ C~1154IA

Suitable high molecular weight polymers include any non..
ionic or anionic water_soluble polymer having a molecular weight of at least 100,000 and preferably at least 1,000,000. Examples of suitable polymers include polyacrylamides such as those set forth in U. S. Patent No. 3,085~j,916, polymers of 2.. acrylamido me'chyl propane sulfonic acid such as those set forth in U. S" Patent No. 3, 709, 816, and sulfonated polystyrenes such as those set forth in U. ~. Patent No. 3, 630, 937.

The invention is further illustrated by the following examples:

10 ppm of a composition comprising a high molecular weight copolymer of 2-acrylamido methyl propane sulfonic acid and acrylamide and a scale inhibitor Camino tris (methylene phosphonate)] in a weight :
ratio of 1:2, 5 was maintained in the water supply to a basic oxygen furnace recycle scrubber syste:m for 13 weeks at which time the .
system was visually inspected and no visible deposition was observed in the pumps, valves or sprays. This is in contrast to heavy fouling ;-~
of pumps, sprays and valves, which resulted in loss of gas washing and cooling efficiencies, thereby causing temporary loss of production, :
that occurred in a two-week period with no treatmentO Previously, ~ :
this system was heavily contaminated with calcium carbonate and -~

contained significant ams:>unts of ferric oxide.
i :
6. 6 ppm of a composition comprising a high molecular weight .

Z5 copolymer of 2.. acrylamido methyl propane sulfonic acid and acrylamide .
':

- 6 _ - : . , 37~D c~ 1 1 54IA

and a scale inhibitor [a~nino tris (methylene phosphonate)] in a weight ratio of 1:2. 5 was maintained in the water supply to a basic oxygen furnace quencher and venturi scrubber system that had a severe build-up of calcium fluoride, iron oxide and calcium carbonate.
After 1600 heats, the system was inspected and the gas ducts~, scupper gratings and nozzles were observed to be clean, ~ 5 ppm of a composition comprising a high molecular weight copolymer of 2.-acrylamido methyl propane sulfonic acid and acrylamide .
and a scale inhibitor Camino tris (methylene phosphonate)] in a weight ratio o 1:2, 5 was maintained in the water supply to a blast furnace scrubber system having heavy iron deposits, which had previously resulted in an increase in the top pressure in the furnace resulting in furnace production loss and shutdown for descaling within one week when a low molecular weight (approximately 1000) polyacrylate and . . ~.
.~ amino tris (methylene phosphonate) were used. After six weeks of . ;
treatment with the high molecular weight polymer/scale inhibitor compositions of this invention, no pressure increase or build_up was .
observed and the system is operating normally.
~.
EXAMPLE 4 :~
` In order to si}nulate conditions in a gas scrubber system, a ~.
synthetic water was prepared which had a pH of 12. 0, a suspended ;:
solids (hydrated ferric oxide) concentration of 2000 mg/l, a sodium hydroxide concentration of 200 mg/l, a sodium bicarbonate concen-tration of 260 mg/l, a calcium concentration of 450 mg/l and a fluoride concentration of 40 mg/l. The water was maintained at a .

7~

temperature of 140+4F. and circulated through the test system at a linear velocity of between 3 and 4 ft. /sec. The test system contained an unheated test section (12 inches long), a heated section (12 inches long), a spray section and a drain section. The inhibitor was added to the synthetic water which was then circulated through the system for five hours at which time the system was shut down and the test sections weighed and the percent inhibition calculated in accordance with the following formula: ~ -rwt. of deposit (inhibited)l % inhibition = 1 - l wt. of deposit (control) ~ x The results of these tests are set forth in Table I.
,, Table I
Weight Gained in Grams ProductConcentration (unheated, heated, %
Test # and Ratio (ppm) drain) Inhibition Control - - 8.21 -8. 325 10. 425 Calgon/ 5, 0 3.29 59. 9 Polymer 1 2. 91 65. 0 1:1 1. 31 87. 4 2 AMP/ 5. 0 0. 88 89. 3 Polymer 1 0. 59 92. 9 1:1 1.16 88.9 3 r~EDP/ 5. 0 1. 67 79. 7 Polymer 1 1.56 81.3 1:1 0 97 90 7 4 Calgon/ 5. 0 0. 50 93. 9 Polymer 2 0. 68 91. 8 1:1 1. 20 88. 5 ~MPj 5. 0 0. 69 91. 6 Polyxner 2 0. 60 92. 8 ` 1:1 1.23 8~.2 -~

' - .
- 8 - ~
''"' ' :, : ~', , , , . . - :, ~7~

Table I (Continued) Weight Gained in Grams ProductConcentration(unheated, heated, %
Test # and Ratio(ppm) drain) Inhibition 6 HEDP/ 5. 0 0. 80 90. 3 Polymer 2 o 55 93 4 1: 1 1. 41 86. 5 .
7 Calgon/ 10. 0 0. 42 94, 9 Polymer 3 0.45 94.6 1:5 1.42 86.4 8 AMP/ 5. 0 8. 35 - 1. 7*
Polymer 3 6.25 24. 9

5:1 11. 54 -10.7* - ~
9 HEDP/ 0. 1 0. 52 93, 7 ~:
Polymer 3 0. 46 94. 5 :
1:1 1.80 82.7 Calgon/ 10. 0 3. 50 57. 4 Polymer 4 3. 31 60. 2 1:5 4.23 59. 4 11 AMP/ 5.0 5.98 27.2 Polymer 4 5. 38 35.4 5:1 f~. 38 38. 8 12 HEDP/ 0. 1 2.21 73. 1 Polymer 4 1. 80 78. 4 1: 1 1. 53 85. 3 13 Calgon/ 0. 1 0. 34 95. 9 Polymer 5 0. 33 96. 0 1:1 0.60 94.2 14 AMP/ 10. 0 1. 49 81. 9 Polymer 5 1. 40 83. 2 :5 *~'c *~ic HEDP/ 5. 0 2. 68 67. 4 Polymer 5 2. 16 74. 1 5:1 1. 99 80. 9 ~'c Values reflect weight gain greater than control value.
** Weights of drain section were not taken since heavy flocculation resulted in more mechanical entrapment than deposit accumulation. -~
. .
:' 7~

Table I (Continued) Weight Gained in Grams ProductConcentration(unheated, heated, %
Test # and Ratio~ppm) drain~ Inhibition 16 Calgon/ 0. 1 0. 62 92. 4 Polymer 6 0. 61 92. 7 1:1 1.65 84.2 17 AMP/ 10. 0 2. 22 73. 0 Polymer 6 2. 07 75. 1 1:5 2.86 72.6 18 HEDP/ 5. 0 4. 31 47. 5 Polymer 6 3. 80 54. 4 5:1 Z.70 74.1 19 Calgon/ 5. 0 0. 43 94. 8 Polymer 7 0. 51 93. 9 5:1 1. 02 90, 2 AMP/ 0. 1 0. 67 91. 8 Polymer 7 0. 57 93. 2 ~ -1:1 0. 44 95. 8 21 HEDP/ 10.0 0. 66 92. 0 Polymer 7 0. 86 89. 7 1:5 1.14 89.1 22 Calgon/ 5. 0 0. 57 93. 1 Polymer 8 0. 58 93. 0 5:1 1.59 84.7 Z3 AMP/ 0. 1 0. 72 91. 2 Polymer 8 0. 51 93. 9 1:1 1.27 87.8 24 HEDP/ 10. 0 1. 84 77. 6 Polymer 8 1. 70 79. 6 115 ~.64 84.3 :

~L~i~37~ c 11 54IA

Pr oduct De signations Calgon sodium hexametaphosphate AMP amino tris (methylene phosphonic acid) HEDP l-hydroxyethylidene~ diphosphonic acid Polymer 1 49/51 copoly~ner of acrylamide and 2-acrylamido-Z-methyl propane-l-sulfonic acid having a molecular weight of appr oximately 1, 000, 000 Polymer 2 homopolymer of 2-acrylamido-2-methyl propane-l-sulfonic acid having a molecular :
weight of approximately S00, 000 Polymer 3 high molecular weight ~mhydrolyzed poly-acrylamide having a molecular weight of .
approximately 1, 000, 000 Polymer 4 low molecular weight sodium acrylate having a molecular weight of approximately 700-1, 000 Polymer 5 high molecular weight hydrolyzed (15%) polyacrylamide having a molecular weight of appr oximately 1, 00 0, 000 : Polymer 6 low molecular weight hydrolyzed (50%) polyacrylamide having a molecular weight of approxi~nately 8, 000 Polymer 7 sulfonated polystyrene having a molecular weight of approximately 700, 000 Polyrner 8 sulfonated polystyrene having a molecular weight c~f apprwrimately 6, 000-8, 000 '; ~
.

.

~. ~ , .. :' -

Claims

The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:

1. A composition useful for controlling deposit build-up in gas scrubbers consisting essentially of a scale inhibitor selected from the group consisting of:
a. phosphonates of the general formula:

wherein R is M is H, NH4, alkali metal or combinations thereof;
n is 0 to 6; and x is 1 to 6;
b. phosphonates of the general formula:

wherein X is -OH or -NH2 and R is an alkyl group of from 1 to 5 carbon atoms; and c. sodium polyphosphates and phosphate esters of the formula:

wherein M may be -H, - NH2 or a monovalent metal ion and R is an alkylene group having from 1 to 18 carbon atoms; and at least one water-soluble polymer selected from the group con-sisting of polyacrylamides, poly(2-acrylamido methyl propane sulfonic acid) and sulfonated polystyrenes, said polymer having a molecular weight of at least 250,000 wherein the ratio of scale inhibitor to polymer is from about 1:10 to about 10:1 by weight.

2. A composition as in Claim 1, wherein the scale inhibitor is amino tris(methylene phosphonate).

3. A composition as in Claim 1, wherein the polymer is a copolymer of acrylamide and 2-acrylamido methyl propane sulfonic acid or its water-soluble salt.

4. A composition as in Claim 1, wherein the polymer is a polyacrylamide.

5. A composition as in Claim 1, wherein the polymer is sulfonated polystyrene.

6. A composition as in Claim 1, wherein the scale inhibitor is a polyphosphate.

7. A composition as in Claim 6, wherein the poly-phosphate is sodium hexametaphosphate.

8. A composition as in Claim 1, wherein the scale inhibitor is a phosphonate of the formula:

wherein X is - OH or - NH2 and R is an alkyl group of from 1 to 5 carbon atoms, or a water-soluble salt thereof.

9. A composition as in Claim 8, wherein the scale inhibitor is hydroxyethylene-1,1-diphosphonic acid or a water-soluble salt thereof.

10. A composition useful for con-trolling deposit build-up in gas scrubbers consisting essentially of amino tris(methylene phosphonate) and a copolymer of acrylamide and 2-acrylamido methyl propane sulfonic acid or its water-soluble salts having a molecular weight of at least 250,000 wherein the weight ratio of phosphonate to polymer is from 1:5 to 5:1.

11. A method of controlling deposit build-up in gas scrubbers which comprises maintaining in the aqueous scrubbing medium at least 0.01 ppm of a composition consisting essentially of a scale inhibitor selected from the group consisting of:
a. phosphonates of the general formula:

wherein R is M is H, NH4, alkali metal or combinations thereof;
n is 0 to 6; and x is 1 to 6;
b. phosphonates of the general formula:

wherein X is -OH or -NH2 and R is an alkyl group of from 1 to 5 carbon atoms; and c. sodium polyphosphates and phosphate esters of the formula:
wherein M may be -H, -NH2 or a monovalent metal ion and R is an alkylene group having from 1 to 18 carbon atoms; and at least one water-soluble polymer selected from the group con-sisting of polyacrylamides, poly(2-acrylamido methyl propane sulfonic acid) and sulfonated polystyrenes, said polymer having a molecular weight of at least 250,000, wherein the ratio of scale inhibitor to polymer is from about 1:10 to about 10:1 by weight.

12. A method as in Claim 11, wherein the polymer is sulfonated polystyrene.

13. A method as in Claim 11, wherein the polymer is a polyacrylamide.

14. A method as in Claim 11, wherein the polymer is a copolymer of acrylamide and 2-acrylamido methyl propane sulfonic acid or its water-soluble salts.

15. A method as in Claim 11, wherein the scale inhibitor is amino tris(methylene phosphonate).

16. A method as in Claim 11, wherein the scale inhibitor is a phosphonate of the formula:

wherein X is -OH or -NH2 and R is an alkyl group of from 1 to 5 carbon atoms, or a water-soluble salt thereof.

17. A method as in Claim 16, wherein -the scale inhibitor is hydroxyethylidene-1,1-diphosphonic acid or a water-soluble salt thereof.

18. A method as in Claim 11, wherein the poly-phosphate is sodium hexametaphosphate.

19. A method as in Claim 11, wherein the scale inhibitor is a polyphosphate.