Source: https://patents.justia.com/patent/10119945
Timestamp: 2019-06-20 01:57:37
Document Index: 457157202

Matched Legal Cases: ['art 1', 'art 1', 'Application No. 13176179', 'Application No. 2012', 'Application No. 2012', 'Application No. 2012']

US Patent for Methods for recovering and analyzing amines Patent (Patent # 10,119,945 issued November 6, 2018) - Justia Patents Search
Justia Patents Peptides Of 3 To 100 Amino Acid ResiduesUS Patent for Methods for recovering and analyzing amines Patent (Patent # 10,119,945)
Jul 16, 2013 - KABUSHIKI KAISHA TOSHIBA
The objects of embodiments in the present disclosure are to provide a method capable of recovering two or more amine compounds at the same time from a gas or solution, and also to provide a method capable of analyzing the recovered amines. The amine-recovering method comprises the steps (A) and (B). In the step (A), the gas or solution is brought into contact with a solid adsorbent so that the adsorbent may retain the amines. In the step (B), the amines retained by the adsorbent in the step (A) are eluted out by use of a basic compound-containing organic solvent. The solid adsorbent has a substituent group represented by —SO3M (M is H or an alkali metal).
As one of the means for carbon dioxide capture and storage (hereinafter, often referred to as “CCS” in the present specification), there is a recovering method based on chemical adsorption. That recovering method has hitherto played an important role in reducing carbon dioxide contained in combustion gases exhausted from boilers in, for example, thermal power plants.
First, a combustion gas exhausted from boilers is subjected to treatments, such as, denitration, dust collection, and desulfurization, according to necessity. The gas is then introduced into an absorption tower, in which the gas is brought into contact with an absorption solution so that CO2 in the combustion gas may be absorbed therein and thereby removed from the combustion gas. The solution thus absorbing CO2 is heated by means of, for example, a heat exchanger, and then introduced into a regeneration tower. In the regeneration tower, CO2 is dissociated and recovered from the absorption solution. After experiencing dissociation of CO2 in the regeneration tower, the absorption solution is circulated again into the absorption tower and reused for absorbing CO2 in the combustion exhaust gas.
wherein said solid adsorbent has a substituent group represented by —SO3M in which M is H or an alkali metal.
In the above method, the solid adsorbent has a substituent group represented by —SO3M (in which M is H or an alkali metal).
Here, “recovering an amine” does not mean simply isolating or removing an aimed amine from the gas or solution, but it means isolating or removing an aimed amine from the gas or solution and then collecting the amine in such a way that the amine does not undergo any essential chemical change between before and after the operations.
If desired, the “amine-recovering method” of the present embodiment enables to recover the amine in a higher concentration than when it was in the gas or solution. In that case, the “amine-recovering method” of the present embodiment can be also regarded as an “amine-concentrating method”.
Preferred examples of the (iii) tertiary amines include: dimethylaminoethanol, diethylaminoethanol, methyl diethanolamine, triethanolamine, 3-(dimethylamino)-1,2-propanediol, 2-{[2-(dimethylamino)ethyl]methylamino}ethanol, N,N,N′,N′-tetramethylethylenediamine, and mixtures of two or more thereof.
The concentration of amine in the gas is not particularly restricted, but is normally 1×10−9 to 1 g/m3, preferably 1×10−8 to 1×10−1 g/m3. The concentration of amine in the solution is not particularly restricted either, but is normally 1 ng/L to 100 mg/L, preferably 10 ng/L to 10 mg/L.
In the step (A) of the “amine-recovering method” according to the present embodiment, a gas or solution containing the aimed amine is brought into contact with a solid adsorbent so that the adsorbent may retain the amine. Here, “the adsorbent may retain the amine” means that the amine and the adsorbent may combine with each other via ionic bonds. Accordingly, if the amine is decomposed or denatured by contact with the solid adsorbent and hence cannot be readily recovered in such original form as was before the procedures, it cannot be said that the adsorbent retains the amine.
It is essential for the solid adsorbent to have a substituent group represented by —SO3M (in which M is H or an alkali metal).
Among the above adsorbents, those having substituent groups represented by —R2—SO3M are preferred and further those having substituent groups represented by —R1—R2—SO3M are particularly preferred. In the above formulas, M is H or an alkali metal; —R1— is a substituent group represented by —[Si(CH3)2]— or —(CH2)n—; and —R2— is a substituent group represented by —(CH2)r—, —(C6H4)s— or —(CH2)t—(C6H4)u—(CH2)v—; provided that n, r, s, t, u and v are integers satisfying the conditions of: 3≤n≤1000, 5≤r≤24, 1≤s≤3, 0≤t≤24, 0≤u≤3, 0≤v≤24 and 2≤(t+u+v).
Preferred —R1— is a substituent group represented by —[Si(CH3)2]— or —(CH2)n—; preferred —R2— is a substituent group represented by —(C6H4)— or —(CH2)—(C6H4)—; and n preferably satisfies the condition of 10≤n≤1000.
The temperature of this step for contact is not particularly restricted and hence is properly determined according to, for example, the kind of the amine, the kind and viscosity of the solution, and the kind of the solid adsorbent. However, it is generally 10 to 40° C.
The step (B) can be carried out at a desired temperature. The temperature is properly determined according to, for example, the kind of the amine, the kind and viscosity of the solution, and the kind of the solid adsorbent. However, it is generally 10 to 40° C.
The “amine-analyzing method” of the present embodiment is characterized by analyzing the amine recovered by the above amine-recovering method of the present embodiment.
The “amine-recovering method” according to the present embodiment is advantageously employed for recovering an amine from an amine-containing gas or solution generated, for example, in CCS processes based on chemical adsorption, and also the “amine-analyzing method” of the present embodiment is useful for analyzing that gas or solution.
Specifically, it is particularly advantageous to employ the methods of the present embodiment for purposes of recovering and analyzing an amine contained in an “amine-containing gas or solution” used intentionally in the CCS processes (for example, an amine component used for preparing an amine-absorption solution) and/or an amine contained in another “amine-containing gas or solution” generated inevitably in the CCS processes (for example, an amine or a degradation product thereof vaporized or leaked out from the CCS apparatuses, such as, a solution-circulating system).
Accordingly, examples of the “amine-containing gas or solution” described above in <<gas or solution containing amine (part 1)>> include both of the “amine-containing gas or solution” used intentionally in the CCS processes and the “amine-containing gas or solution” generated inevitably in the CCS processes.
In the present embodiment, the “amine-containing gas or solution” contains an amine and water. It contains at least one amine, and may contain two or more amines. Preferably, it contains two to four kinds of amines. If two or more kinds of amines are used, they bring complementary effects that only one amine cannot realize and, as a result, they may improve performance of carbon dioxide capture and storage. On the other hand, if too many kinds of amines are used, it is often difficult to keep the performance in view of the apparatus operation. The amines are described above in <<gas or solution containing amine (part 1)>> in detail.
the step (α), in which a gas containing carbon dioxide is brought into contact with an absorption solution containing an amine and water so that the absorption solution may absorb the carbon dioxide, and
the step (β), in which the carbon dioxide absorbed in the absorption solution in the above step (α) is dissociated from the solution.
In the step (α), a carbon dioxide-containing gas, for example, a combustion gas from fossil fuel (such as, coal, petroleum, or LNG), is brought into contact with an absorption solution containing an amine and water so that the absorption solution may absorb the carbon dioxide. In this step, it is possible to adopt known carbon dioxide-absorbing systems, such as, a dispersed gas type-absorbing apparatus comprising a bubble agitation tank and a bubble tower, and a dispersed liquid type-absorbing apparatus comprising a spray tower, a spray chamber, a scrubber, a wetted wall tower, and a packed tower. In those systems, the carbon dioxide-containing gas can be brought into contact with the absorption solution containing an amine and water. In view of the carbon dioxide absorption efficiency, it is preferred to use a carbon dioxide-absorption tower filled with filler.
This step may be carried out at any reaction temperature as long as carbon dioxide can be absorbed. However, in view of the absorption rate and the absorption efficiency, the reaction temperature is preferably 25° C. to 70° C. inclusive, more preferably 30° C. to 60° C. inclusive.
In the step (β), the carbon dioxide absorbed in the absorption solution containing an amine and water in the above step (α) is dissociated from the solution. As means for dissociating the carbon dioxide from the absorption solution containing an amine and water, the treatments of pressure reduction, heating and membrane separation are employable. However, they by no means restrict this step. However, the carbon dioxide can be easily dissociated by heating treatment. The heating treatment may be carried out at any temperature as long as the carbon dioxide can be dissociated, but the temperature is preferably 40° C. to 150° C. inclusive, more preferably 70° C. to 140° C. inclusive.
Preferred examples of the amines to which the “amine-recovering method” of the present embodiment can be applied include those used in the above carbon dioxide-recovering method comprising the steps (α) and (β).
Further, preferred examples of the “amine-analyzing method” according to the present embodiment include a method for analyzing the amines recovered by the above carbon dioxide-recovering method comprising the steps (α) and (β).
The procedure of Example 1 was repeated except for employing 5 mL of an aqueous solution containing 0.1 vol % of phosphoric acid and nitrosodimethylamine, nitrosodiethylamine, nitrosodiethanolamine, nitrosopiperazine, nitrosopiperidine, monoethanolamine, diethanolamine, methyl diethanolamine, 2-amino-2-methylethanol, methylaminoethanol, piperazine, piperidine, and morpholine each in an amount of 10 μg/mL, to recover and analyze the amines. The results were shown in Table 2.
The procedure of Example 1 was repeated except for employing 50 mL of an aqueous solution containing 0.1 vol % of phosphoric acid and nitrosodimethylamine, nitrosodiethylamine, nitrosodiethanolamine, nitrosopiperazine, nitrosopiperidine, monoethanolamine, diethanolamine, and methyl diethanolamine each in an amount of 1 μg/mL, to recover and analyze the amines. The results were shown in Table 3.
The procedure of Example 1 was repeated except for employing 5 mL of an aqueous solution containing 0.1 vol % of phosphoric acid, 100 mg of pulverized coal, 0.1 mL of methanol, 100 ppm of iron ions, and nitrosodimethylamine, nitrosodiethylamine, nitrosodiethanolamine, nitrosopiperazine, nitrosopiperidine, monoethanolamine, diethanolamine, and methyl diethanolamine each in an amount of 10 μg/mL, to recover and analyze the amines. The results were shown in Table 3.
The procedure of Example 1 was repeated except for employing 5 mL of an aqueous solution containing 5 vol % of phosphoric acid and nitrosodimethylamine, nitrosodiethylamine, nitrosodiethanolamine, nitrosopiperazine, nitrosopiperidine, monoethanolamine, diethanolamine, methyl diethanolamine, piperazine, and piperidine each in an amount of 10 μg/mL, to recover and analyze the amines. The results were shown in Table 3.
The procedure of Example 1 was repeated except for replacing the solid adsorbent with another solid adsorbent having a substituent group of —O—Si(CH3)2—C3H6—SO3Na, to recover and analyze the amines. The results were shown in Table 4.
nitrosodimethylamine 9.7 9.8 9.5 9.6 9.8 9.7 9.8 nitrosodiethylamine 9.5 9.6 9.4 9.6 9.4 9.8 9.4 nitrosodiethanolamine 9.8 9.8 9.6 9.8 9.6 9.6 9.6 nitrosopiperazine 10 9.9 9.9 9.8 9.7 9.9 9.8 nitrosopiperidine 9.8 9.5 9.6 9.6 10 9.7 9.9 monoethanolamine 9.7 9.6 9.4 9.7 9.5 9.5 9.5 diethanolamine 9.6 9.8 9.5 9.5 9.8 9.8 9.8 methyl diethanolamine 9.7 9.8 9.4 9.4 9.7 9.7 9.9 2-amino-2- — — — — — — — methylethanol methylaminoethanol — — — — — — — piperazine — — — — — — — piperidine — — — — — — — morpholine — — — — — — — recovered concentration [μg/mL]
TABLE 2 Ex. Ex. Ex. Ex. Ex. 8 Ex. 9 10 11 12 13 Ex. 14
nitrosodimethylamine 9.7 9.7 9.8 9.6 9.7 9.6 9.8 nitrosodiethylamine 9.8 9.8 9.9 9.7 9.6 9.8 9.6 nitrosodiethanolamine 9.6 9.9 9.6 9.8 9.8 9.7 9.9 nitrosopiperazine 9.9 9.9 10 9.9 9.9 9.8 10 nitrosopiperidine 9.8 9.6 9.9 9.5 9.6 9.8 9.8 monoethanolamine 9.5 9.8 9.7 9.6 9.8 9.5 9.7 diethanolamine 9.6 9.8 9.6 9.8 9.9 9.7 9.6 methyl diethanolamine 9.7 9.9 9.8 9.9 9.7 9.6 9.8 2-amino-2-methylethanol — — — — — — 9.6 methylaminoethanol — — — — — — 9.8 piperazine — — — — — — 9.9 piperidine — — — — — — 9.6 morpholine — — — — — — 9.8 recovered concentration [μg/mL]
TABLE 3 Ex. Ex. Ex. Ex. Ex. 15 Ex. 16 Ex. 17 18 19 20 21
nitrosodimethylamine 9.8 9.9 9.8 9.7 9.8 6.5 0.2 nitrosodiethylamine 9.6 9.7 9.7 9.6 9.9 7 0.1 nitrosodiethanolamine 9.7 9.8 9.6 9.4 9.7 5.9 0.2 nitrosopiperazine 9.9 10 9.8 9.8 9.9 6.8 0.6 nitrosopiperidine 9.8 9.8 9.8 9.4 9.8 7.5 0.9 monoethanolamine 9.6 9.9 9.7 9.6 9.7 6.3 0.7 diethanolamine 9.8 9.7 9.8 9.8 9.8 4.8 0.6 methyl diethanolamine 9.7 9.8 9.7 9.7 9.6 5.5 0.2 2-amino-2-methylethanol — — — — — — — methylaminoethanol — — — — — — — piperazine — — — — — 9.5 — piperidine — — — — — 8.7 — morpholine — — — — — — — recovered concentration [μg/mL]
TABLE 4 Ex. 22 Ex. 23 Com. 1 Com. 2
nitrosodimethylamine 8.7 9.5 1.8 0.9 nitrosodiethylamine 8.2 9.6 2.3 3.1 nitrosodiethanolamine 7.8 9.7 0.9 2.6 nitrosopiperazine 9.3 9.9 3.6 2.5 nitrosopiperidine 7.4 9.4 2.4 3 monoethanolamine 5.8 9.4 1.8 1.7 diethanolamine 6.9 9.3 5.8 6.4 methyl diethanolamine 8.2 9.8 6.3 5.8 2-amino-2-methylethanol — — — — methylaminoethanol — — — — piperazine — — — — piperidine — — — — morpholine — — — — recovered concentration [μg/mL]
1. A method for recovering at least one nitrosamine contained in a solution, comprising:
controlling a pH value of solution in the range of from 1 to 7 and bringing the solution into contact with a solid adsorbent packed in a cartridge or column so that the solid adsorbent retains the at least one nitrosamine, the solid adsorbent comprising an adsorbent support and a substituent group combining with the adsorbent support, said adsorbent support being selected from the group consisting of silica gel, alumina, glass, kaolin, mica, talc, hydrated alumina, Wollastonite, iron powder, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, calcium carbonate, carbon, barium sulfate, boron, ferrite, cellulose, and activated carbon, and
said substituent group being represented by —(CH2)w—C6H4—SO3H or —Si(CH3)2—CH2—C6H4—SO3H, wherein w is an integer satisfying the condition of 4≤w≤1000; and
eluting out the at least one nitrosamine retained by the solid adsorbent with a basic compound-containing organic solvent, wherein said eluting is performed while applying a pressure,
wherein the organic solvent is selected from the group consisting of methanol, ethanol, 2-propanol, and acetone.
wherein the basic compound-containing organic solvent is methanol comprising ammonia in an amount of 0.5 to 10 wt %.
wherein the basic compound-containing organic solvent further comprises:
an aqueous solution comprising an acid in an amount of 5 wt % or less.
wherein the solid adsorbent is in the form of a column.
wherein the at least one nitrosamine was previously used in a carbon dioxide-recovering method comprising:
bringing a gas containing carbon dioxide into contact with a basic absorption solution so that the basic absorption solution absorbs the carbon dioxide, and
dissociating the carbon dioxide absorbed in the basic absorption solution from the basic absorption solution.
analyzing at least one nitrosamine recovered;
wherein the at least one nitrosamine is analyzed in a manner selected from the group consisting of high performance liquid chromatography, high performance liquid chromatography-mass spectrometry, gas chromatograph flame ionization detection, and gas chromatograph-mass spectrometry.
wherein the at least one nitrosamine is in the solution.
wherein the substituent group of the solid adsorbent is —(CH2)w—C6—SO3H wherein w is an integer satisfying the condition of 4≤w≤1000.
wherein the substituent group of said solid adsorbent is Si(CH3)2—CH2—C6H4—SO3H.
wherein the solution further comprises at least one additional amine.
wherein the pH of solution is from 1 to 5.
wherein said basic compound-containing organic solvent further comprises:
an aqueous solution comprising phosphoric acid in an amount of 5 wt % or less.
wherein a basic compound of the basic compound-containing organic solvent is not a pyridine.
5451660 September 19, 1995 Builder
8506913 August 13, 2013 Murai
20080207638 August 28, 2008 Ancliff et al.
20090018029 January 15, 2009 Miao
20100108610 May 6, 2010 Godhwani et al.
S49-84977 August 1974 JP
10-90240 April 1998 JP
11-90160 April 1999 JP
4101463 June 2008 JP
2009-501744 January 2009 JP
2011-521781 July 2011 JP
2012-223681 November 2012 JP
WO 2009/145372 December 2009 WO
WO 2011/027794 March 2011 WO
WO 2011/121633 October 2011 WO
Ancliff et al. Compounds. WO 2007/009739.
Singh, N. et al. Benzimidazole: A short review of their antimicrobial activites.(2012). 5:119-127.
Extended European Search Report dated Sep. 27, 2013 in Patent Application No. 13176179.3.
Pavel Jandera, et al, “Ion-Exchange Chromatography of Nitrogen Compounds” Journal of Chromatography, vol. 98, No. 1, XP055079494, Mar. 1, 1974, pp. 1-54.
Donald J. Pietrzyk, “Ion-Exchange Resins in Non-Aqueous Solvents—I,” Talanta, vol. 13, No. 2, XP026580513, Feb. 1, 1966, pp. 209-223.
Vida Simat, et al., “Use of small diameter column particles to enhance HPLC determination of histamine and other biogenic amines in seafood” LWT—Food Science and Technology, vol. 44, No. 2, XP027445449, Mar. 1, 2011, pp. 399-406.
Office Action dated Jun. 13, 2014 in Japanese Patent Application No. 2012-159628 (with English translation).
Japanese Office Action dated Feb. 10, 2015 in corresponding Japanese Patent Application No. 2012-159628 filed Jul. 18, 2012 (with English translation).
Office Action dated Apr. 12, 2016 in Japanese Patent Application No. 2012-159628 (with unedited computer generated English language translation).
Patent Publication Number: 20140024127
Inventors: Hiroko Watando (Tokyo), Takashi Kuboki (Tokyo)
Application Number: 13/942,954
International Classification: G01N 30/96 (20060101); C07C 213/10 (20060101); B01D 15/00 (20060101); C07C 241/00 (20060101); B01D 53/14 (20060101); B01J 39/17 (20170101); B01J 49/06 (20170101); B01J 49/53 (20170101); B01J 49/60 (20170101);