CN1718615A

CN1718615A - Humic acid and humin classification continuous extraction method in the soil

Info

Publication number: CN1718615A
Application number: CN 200410011003
Authority: CN
Inventors: 刘居东; 邢宝山; 韩晓增
Original assignee: Northeast Institute of Geography and Agroecology of CAS
Current assignee: Northeast Institute of Geography and Agroecology of CAS
Priority date: 2004-07-23
Filing date: 2004-07-23
Publication date: 2006-01-11

Abstract

The invention belongs to a kind of extracting method of the soil organism in the field of agricultural production technologies, is exactly a kind of humic acid (Humic acid) in the soil organism and novel method of humin (Humin) extracted specifically.The present invention has improved the moiety of traditional extraction mixed solution, has reduced the probability of extract generation alkaline hydrolysis; Another key point is in the process of extracting extract to be separated, and process and the sample classification that extracts combined together, finally obtains a plurality of classification samples rather than one, thereby better meets the scientific research needs.

Description

Humic acid and humin classification continuous extraction method in the soil

Technical field

The invention belongs to a kind of extracting method of the soil organism in the field of agricultural production technologies, is exactly a kind of humic acid (Humic acid) in the soil organism and novel method of humin (Humin) extracted specifically.

Technical background

Humic acid and humin are the chief components of the soil organism, and its main component is the macromolecule organic mixture.The situation of the soil organism is determining physics, the chemistry and biology characteristic of soil in the soil, has also determined the healthy state and the soil productivity of soil.Therefore, the researchist of soil science both domestic and external aspect to the soil organism research all pay much attention to.Humic acid and humin form focus and breach into soil research work as the core component of the soil organism.

The traditional extraction humic acid and the method for humin generally adopt the mixing solutions of sodium hydroxide solution or sodium hydroxide and trisodium phosphate, pedotheque is carried out 1 time extract or extract several times the back mixed extract, the mixed extract that obtains advanced to separate again purifies, and obtains 1 humic acid sample; Obtain 1 humin sample through handling again through extracting the remaining soil residuals in back.Therefore also can only obtain single information after analyzing and measure for humic acid or humin.Because humic acid and humin are the mixtures of the organic high molecular compound of high complexity, molecular structure is closely similar again in its moiety, and this has just caused the difficulty of separating and analyzing.Best terms of settlement is that humic acid and humin are carried out high separation, make it become the component of single chemical structure one by one, but present scientific and technical means can't be accomplished this point, is present effective and feasible approach so it is carried out the part separation.

Summary of the invention

The present invention repeatedly extracts same pedotheque continuously from this angle, and the extracting solution that obtains is handled respectively, obtains the different humic acid classification sample of a plurality of physicochemical property; The extraction of humin obtains by remaining soil residuals after extracting humic acid, the dark part in the upper strata of soil residuals is obtained 2 humin studies with lower floor's light-colored part after separating, just obtained 2 humin samples through after a series of purification process respectively again.

Key of the present invention is in the process of extracting extract to be separated, and the process of extraction and the classification of sample are combined together, finally obtains a plurality of graded products, thereby better meets the scientific research needs.

Technical scheme

The present invention adopts sodium pyrophosphate solution that pedotheque is extracted, and does not use the sodium hydroxide commonly used in the traditional method or the mixed solution of sodium hydroxide and trisodium phosphate, and is strong excessively with the alkalescence of avoiding extracting solution, thereby reduces the probability of extract generation alkaline hydrolysis.Extract is carried out multiple extraction, rather than extract for traditional 1 time or 2-3 time, guaranteed that extract is extracted fully.Extracting solution after the extraction is handled respectively one by one, not to handle again after mixing, can obtain the classification sample of different extraction times like this, this step is very crucial, can't again it be separated because the sample that extracts is in a single day mixed, and the sample that extracts each time all has different physicochemical property and constitutional features, these characteristics are extremely important for the researchist, can see Changing Pattern between extract and extraction time by instrumental analysis, and then analyze the different differences of dividing inter-stage of contained humic acid of this pedotheque and humin.

The grading extraction step:

1. early-stage preparations: the A pedotheque is crossed the 2mm sieve; B configuration extraction liquid: the sodium pyrophosphate solution of 0.1M.

2. extract: pedotheque was mixed the sealing in 5 minutes of logical nitrogen, concussion, 5-12 hour with 1: 7 with extracting solution.

3. separate: centrifugation, 4000 changeed 10-30 minute, shifted out the upper strata liquid stillness of night to place other container pending.

4. extract: the lower soil sample returns extraction vessel again, repeating step 2-3, and multiplicity is a particular case and decide, advises more than 10 times.

The humic acid treatment step:

1. add 6N HCl in the clear liquid that obtains, accent pH is 1-2, obtains precipitation, and is centrifugal after the most of supernatant liquor of sucking-off.

2. will precipitate and be dissolved in again in the sodium pyrophosphate solution, recentrifuge is removed residue, obtains supernatant liquor.

3. repeating step 1-2 is two to three times.

4. with step 1.

5. add 0.3/0.1M HF/HCl mixed solution in throw out, washing precipitation is washed 3-4 time, and each washing all will be stirred or shake 4-8 hour.

6. washing back centrifugation, precipitation are with distilled water or weak salt acid elution 3-4 time, and it is rapid that washing is wanted.

7. lyophilize.

The humin treatment step:

1. will extract behind the humic acid remaining soil residuals with distilled water wash 3-5 time.

2. wash for the last time and can be observed precipitation after centrifugal and be divided into two-layerly up and down substantially, the upper strata color is darker, and lower floor is more shallow.It is changed over to respectively in two plastic beakers.

3. in two beakers, add 3M HF solution, put into magnetic stirring bar, stirring or concussion 4-8 hour.

4. centrifugal, fall to remove the upper strata stillness of night, repeating step 3-4, multiplicity is fixed according to particular case, is generally 4-6 time.

5. with distilled water wash precipitation, 3-5 time, lyophilize.

Description of drawings: Fig. 1 is a process flow sheet of the present invention.

Embodiment

The present invention must be application in Hundred Talents Program (functional effect of organic matter in black soil aspect agricultural sustainable development and the environment protection) problem of Northeast Institute of Geography and Agricultural Ecology, Chinese Academy of Sc.By present method Chinese Heilungkiang black earth has been carried out the extraction of humic acid and humin in the carrying out of problem, obtained good effect, concrete situation is as follows:

Pedotheque is done 23 times extracted, obtained 23 humic acids and 2 humin samples.And resulting sample is analyzed with analysis means such as fourier infrared, ultraviolet, ultimate analysis, nucleus magnetic resonance.

Table 1. a results of elemental analyses and atom percentage

Name	N	C	H	O	Ash	C/H	C/O
Name	N	C	H	O	Ash	C/H	C/O	F-1	2.82	52.41	3.55	35.98	5.24	1.24	1.94
F-3	3.22	54.13	3.71	36.94	2.00	1.22	1.95	F-1	2.82	52.41	3.55	35.98	5.24	1.24	1.94
F-3	3.22	54.13	3.71	36.94	2.00	1.22	1.95	F-4	3.42	53.66	4.21	36.59	2.12	1.07	1.95
F-6	3.39	53.27	4.44	36.51	2.38	1.01	1.94	F-4	3.42	53.66	4.21	36.59	2.12	1.07	1.95
F-6	3.39	53.27	4.44	36.51	2.38	1.01	1.94	F-7	3.18	54.10	4.64	35.14	2.94	0.98	2.05
F-12	3.59	54.26	5.16	34.91	2.08	0.88	2.07	F-7	3.18	54.10	4.64	35.14	2.94	0.98	2.05
F-12	3.59	54.26	5.16	34.91	2.08	0.88	2.07	F-14	3.62	54.45	5.08	32.93	3.92	0.90	2.20
F-16	3.48	55.77	5.66	33.19	1.91	0.83	2.24	F-14	3.62	54.45	5.08	32.93	3.92	0.90	2.20
F-16	3.48	55.77	5.66	33.19	1.91	0.83	2.24	F-18	3.33	48.16	5.08	29.98	13.45	0.80	2.14
F-21	3.21	50.32	5.70	28.87	11.90	0.74	2.32	F-18	3.33	48.16	5.08	29.98	13.45	0.80	2.14
F-21	3.21	50.32	5.70	28.87	11.90	0.74	2.32	H-2	0.16	2.80	0.34	1.89	94.81	0.68	1.97

From table 1, has significant otherness between our each as can be seen sample that proposes, and the clear regularity variation is arranged, we can obtain more information by infrared analysis, ultra-violet analysis and nuclear magnetic resonance spectroscopy, as the Changing Pattern of aromatic carbon and alkyl carbon, Changing Pattern of optical density(OD) or the like.Because this subject study still in the middle of carrying out, is not easy to openly too many relevant concrete data, but only just can be with absolute predominance and the practicality that embodies present method from last table.

Claims

1, in the soil organism extracted, a kind of method of extracting humic acid and humin is characterized in that adopting the extracting solution of sodium pyrophosphate solution as pedotheque; In leaching process, extract is separated, the process and the classification of extracting combined together, finally obtain a plurality of classification samples.

2, the method for telling according to claim 1, its feature has adopted following concrete steps

The grading extraction step:

A. early-stage preparations: the A pedotheque is crossed the 2mm sieve; B configuration extraction liquid: the sodium pyrophosphate solution of 0.1M;

B. extract: pedotheque was mixed the sealing in 5 minutes of logical nitrogen, concussion, 5-12 hour with 1: 7 with extracting solution;

C. separate: centrifugation, 4000 changeed 10-30 minute, shifted out the upper strata liquid stillness of night to place other container pending;

D. extract: the lower soil sample returns extraction vessel again, repeating step 2-3, and multiplicity is a particular case and decide, advises more than 10 times;

The humic acid treatment step:

A. add 6N HCl in the clear liquid that obtains, accent pH is 1-2, obtains precipitation, and is centrifugal after the most of supernatant liquor of sucking-off;

B. will precipitate and be dissolved in again in the sodium pyrophosphate solution, recentrifuge is removed residue, obtains supernatant liquor;

C. repeating step 1-2 is two to three times;

D. with step 1;

E. add 0.3/0.1M HF/HCl mixed solution in throw out, washing precipitation is washed 3-4 time, and each washing all will be stirred or shake 4-8 hour;

F. washing back centrifugation, precipitation are with distilled water or weak salt acid elution 3-4 time, and it is rapid that washing is wanted;

G. lyophilize;

The humin treatment step:

A. extract behind the humic acid remaining soil residuals with distilled water wash 3-5 time;

B. can be observed precipitation after last washing is centrifugal and be divided into two-layerly up and down substantially, the upper strata color is darker, and lower floor is more shallow.It is changed over to respectively in two plastic beakers;

C. in two beakers, add 3M HF solution, put into magnetic stirring bar, stirring or concussion 4-8 hour;

D. centrifugal, fall to remove the upper strata stillness of night, repeating step 3-4, multiplicity is fixed according to particular case, is generally 4-6 time;

E. with distilled water wash precipitation, 3-5 time, lyophilize.