CN102425018B

CN102425018B - Dermal collagen fiber prepared from tanning chromium-containing subsidiary waste

Info

Publication number: CN102425018B
Application number: CN2011103269020A
Authority: CN
Inventors: 但卫华; 胡杨; 周华龙; 但年华; 叶光斗; 李建新
Original assignee: Sichuan University
Current assignee: Sichuan University
Priority date: 2011-10-25
Filing date: 2011-10-25
Publication date: 2013-11-20
Anticipated expiration: 2031-10-25
Also published as: CN102425018A

Abstract

本发明公开了一种利用制革含铬副废物制备的真皮胶原纤维及其制备方法，该方法是以制革含铬副废物为原料，在保证胶原纤维良好的物理机械条件不变的前提下，采用物理、化学和生化相结合的方法，对制革含铬副废物进行蓬松、解纤、分纤及梳理等处理，制备得到性能优良、用途广泛的真皮胶原纤维。此真皮胶原纤维达到以下技术指标：（1）外观为淡蓝色纤维状物，无肉眼所见之杂质；（2）水分含量在18-25%之间；（3）线密度在1.2-2.0dtex之间；（4）纤维长度在20-30mm之间；（5）断裂强度≥3.5cN/tex；（6）断裂伸长率在10-30%之间；（7）回潮率在6-10%之间。这种真皮胶原纤维可以用作高仿真皮革（汽车座椅革、家具革、鞋面革、服装革、鞋里革、皮带革、箱包革等）、真皮基布、高级地毯、高级墙纸以及真皮纤维被褥等的原料。The invention discloses a dermis collagen fiber prepared by utilizing the chromium-containing by-products of tanning and a preparation method thereof. The method uses the chromium-containing by-waste of tanning as a raw material and ensures that the good physical and mechanical conditions of the collagen fibers remain unchanged. In this paper, by combining physical, chemical and biochemical methods, the chromium-containing by-products of tanning are fluffed, defibrated, divided and carded, and the dermal collagen fibers with excellent performance and wide application are prepared. The dermal collagen fibers meet the following technical indicators: (1) The appearance is light blue fibrous matter, without impurities visible to the naked eye; (2) The moisture content is between 18-25%; (3) The linear density is 1.2-2.0 Between dtex; (4) fiber length between 20-30mm; (5) breaking strength ≥ 3.5cN/tex; (6) breaking elongation between 10-30%; (7) moisture regain between 6- Between 10%. This kind of genuine leather collagen fiber can be used as high imitation leather (car seat leather, furniture leather, upper leather, clothing leather, shoe lining leather, belt leather, bag leather, etc.), genuine leather base cloth, high-grade carpet, high-grade wallpaper and real leather Raw materials for fiber quilts, etc.

Description

A kind of dermal collagen fiber that utilizes process hides to contain the secondary refuse preparation of chromium

Technical field

The present invention relates to a kind of dermal collagen fiber that process hides contains the secondary refuse preparation of chromium and preparation method thereof that utilizes, belong to the industry light industry textile industry field.

Background technology

It is one of long-term unsolved public hazards of leather industry that process hides contains the secondary refuse of chromium.Over more than 100 year, chrome tanning occupies dominant position in leather industry always.Have data to show, in the process hides process, have about 30% raw material skin to become to contain the secondary refuse of chromium (Nie Linshan, Qiang Xihuai, Zhang Chuanbo. the progress [J] that the secondary refuse of Leather Factory is processed. Environmental Pollution and Control .2001,23(5): 268-270).The present leather output of China accounts for global 20-25%, and, to cut open wet blue leather as main, it is estimated, approximately produce every year 50-70 ten thousand tons (weight in wet bases) contain the secondary refuse of chromium (Lin Wei ，Mu Chang road, Zhang Mingrang. the secondary changing waste into resources of leather (

) [J]. Chinese leather .2002,31(13): 37-41).The generation that contains the secondary refuse of chromium has not only caused the significant wastage of raw material skin resource, but also has brought serious problem of environmental pollution.Therefore, process hides contains the resource of the secondary refuse of chromium, for taking full advantage of raw material skin resource, alleviate and even eliminate pollution in leather industry, realize recycling economy, all is significant.

The leather technology worker is doing a large amount of work aspect the recycling that contains the secondary refuse of chromium both at home and abroad, and has obtained many impressive progresses.In early days, people utilize and contain the secondary refuse production of chromium regenerated leather, non-weaving cloth and porous adsorbing material etc., extract all kinds of hydrolytic collagens of preparation, polypeptide, and, as raw material, produce leather finishing agent, fatting agent, tanning agent and surfactant etc.In the last few years, people had researched and developed multiple method of taking off chromium, on the one hand, the chromium that contains in the secondary refuse of chromium were recycled, and on the other hand, can also extract industrial gelatine from contain the secondary refuse of chromium, had improved widely the added value that contains the secondary refuse of chromium.According to Introduction of Literatures, the leftover pieces of shoe lining leather, suede garment leather, glace kid leather especially are fit to the production of non-weaving cloth, adopt wet method, the fine method of segmentation continuous solution, can make more than fibre length more than 70% reaches 25mm.Relevant technique it is not yet seen bibliographical information.Up to now, utilize Treatment agent of compound enzyme skin sollagen F, in conjunction with wet method fluffy technology, produce the dermal collagen fiber from the secondary refuse of process hides, not yet see both at home and abroad report (but Wei Hua chief editor, Wang Kunyu associate editor. the light industry clearer production technology. Beijing: the .2008:119-147 of China Textiles Press).

In sum, prior art has the following disadvantages:

1. prior art has certain restriction to the source that contains the secondary refuse of chromium, and much containing the secondary refuse of chromium can not be effectively utilized, thereby can't realize containing whole digestion of the secondary refuse of chromium;

2. adopt prior art to process and contain the secondary refuse of chromium, more than resulting fibre length failed to reach 25mm fully, Application Areas was very limited, and had restricted the resource that contains the secondary refuse of chromium;

3. prior art solution fibre is not yet realized industrialization and commercialization.

Summary of the invention

The objective of the invention is the deficiency that exists for prior art and provide a kind ofly utilize process hides to contain the secondary refuse of chromium to prepare the method for dermal collagen fiber, be characterized in take leather industry contain the secondary refuse of chromium as raw material, preparation has the dermal collagen fiber than high added value.The method comprises the following steps:

1. weigh: the process hides of accurately weighing contains the secondary refuse (hereinafter to be referred as secondary refuse) of chromium, as the meter material foundation of following each operation.

2. ease back, acidifying, enzyme process: (1) technical stipulation: water 50-200%, initial in temperature: normal temperature, penetrating agent JFC 0.1-0.5%, oxalic acid 1.0-5.0%, Treatment agent of compound enzyme skin sollagen F 0.10-0.40%.(2) method of operating: after mixing up liquor ratio, interior temperature, add penetrating agent JFC, oxalic acid, rotate 10-40min, add Treatment agent of compound enzyme skin sollagen F, rotate 30-90min, stop 10-60min, rotate 10-60min, open drum inspection, terminal pH=2.4 ±, interior temperature≤40 ℃.

3. neutralization: (1) technical stipulation: water 50-200%, interior temperature 30-45 ℃, sodium bicarbonate 0.5-1.5%.(2) method of operating: after mixing up liquor ratio, interior temperature, add sodium bicarbonate, rotate 30-120min, open drum inspection, terminal pH=5.0-6.5.

4. go out drum: after neutralization reaches requirement, secondary refuse is gone out drum, entrucking, enter and separate fine operation.

5. separate fine, water squeezing: separate fibre on fiber uncoiling machine, directly water squeezing after solution is fine.Require the thorough destructing of secondary refuse, the noresidue skin bit, separate non-foam in fine process and produce.After water squeezing, the fiber cake moisture of gained is 60-70%.

6. dry: as to adopt the method for airing, moisture: 30-35%.

7. returning property: after moisture reaches requirement, the fiber cake is collected the 1-2 days that banks up, with equilibrium water conten.Note, the fiber cake time of banking up must not be over 10 days.

8. weigh: the fiber cake is accurately weighed, as the meter material foundation of following each operation.

9. vexed oil is opened fibre: (1) technical stipulation: interior temperature normal temperature, water 5-20%, compound oil Z-15 1.0-4.0%.(2) method of operating: first the fiber cake is joined in rotary drum, then add normal-temperature water and emulsification in advance grease completely, rotate 10-60min and get final product.

10. go out drum: after vexed oil is opened fibre and reached requirement, fluffy crude fibre is gone out drum, entrucking, enter next procedure.

11. shredding: carry out on opener.Require tentatively with the corium fabric of mat separation and loose.

12. minute fibre: carry out on minute fine machine.Require further to separate and loose dermal collagen fiber, without the entanglement phenomenon.

13. carded: carry out on carding machine.Situation loose according to the separation of dermal collagen fiber, carded 1-2 road.Require the dermal collagen cellulose floss to scatter, without the entanglement phenomenon.

14. combing: carry out on combing machine.Situation loose according to the separation of dermal collagen fiber, combing 1-3 road, namely obtain the dermal collagen fiber.

Rotary drum is the wooden rotary drum of suspension type or stainless steel rotary drum.

The main performance of the resulting dermal collagen fiber of the present invention:

1. outward appearance: light blue fibrous material, without the impurity of finding of naked eye;

2. moisture (%): 18-25;

3. line density (dtex): 1.2-2.0;

4. fibre length (mm): 20-30;

5. fracture strength (cN/tex): 〉=3.5;

6. elongation at break (%): 10-30;

7. regain (%): 6-10.

The prepared dermal collagen fiber of method of the present invention, can be used as the raw material of high emulational leather (automotive seat leather, furniture leather, upper leather, clothing leather, shoe lining leather, belt leather and luggage leather etc.), corium base cloth, senior carpet, senior wallpaper and corium bed clothes etc.

The present invention has the following advantages:

1. contain the secondary refuse of chromium with process hides cheap and easy to get, wide material sources, prepare the dermal collagen fiber, turn waste into wealth, turn harm into good,, for whole leather industry realizes recycling economy, established solid foundation;

2. technological specification, condition is controlled, is easy to suitability for industrialized production;

3. this method also can be used for the processing of Leather-goods Industry tailing;

4. basically do not produce secondary pollution in production process, have significant ecological benefits, environmental benefit and economic benefit.

The specific embodiment

Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this; the present embodiment only is used to further illustrate the present invention; and can not be interpreted as that to the restriction of the protection domain of invention, the person skilled in the art in this field can content according to the present invention make some nonessential improvement and adjustment.

Embodiment 1

2. ease back, acidifying, enzyme process: (1) technical stipulation: water 50%, initial in temperature: normal temperature, penetrating agent JFC 0.1%, oxalic acid 1.0%, Treatment agent of compound enzyme skin sollagen F 0.10%.(2) method of operating: after mixing up liquor ratio, interior temperature, add penetrating agent JFC, oxalic acid, rotate 10min, add Treatment agent of compound enzyme skin sollagen F, rotate 30min, stop 10min, rotate 10min, open drum inspection, terminal pH=2.4 ±, interior temperature≤40 ℃.

3. neutralization: (1) technical stipulation: water 50%, 30 ℃ of interior temperature, sodium bicarbonate 0.5%.(2) method of operating: after mixing up liquor ratio, interior temperature, add sodium bicarbonate, rotate 30min, open drum inspection, terminal pH=5.0-6.5.

6. dry: as to adopt the method for airing, moisture: 30-35%.

9. vexed oil is opened fibre: (1) technical stipulation: interior temperature normal temperature, water 5%, compound oil Z-15 1.0%.(2) method of operating: first the fiber cake is joined in rotary drum, then add normal-temperature water and emulsification in advance grease completely, rotate 10min and get final product.

Embodiment 2

2. ease back, acidifying, enzyme process: (1) technical stipulation: water 120%, initial in temperature: normal temperature, penetrating agent JFC 0.3%, oxalic acid 3.0%, Treatment agent of compound enzyme skin sollagen F 0.30%.(2) method of operating: after mixing up liquor ratio, interior temperature, add penetrating agent JFC, oxalic acid, rotate 30min, add Treatment agent of compound enzyme skin sollagen F, rotate 60min, stop 40min, rotate 40min, open drum inspection, terminal pH=2.4 ±, interior temperature≤40 ℃.

3. neutralization: (1) technical stipulation: water 120%, 38 ℃ of interior temperature, sodium bicarbonate 1.0%.(2) method of operating: after mixing up liquor ratio, interior temperature, add sodium bicarbonate, rotate 80min, open drum inspection, terminal pH=5.0-6.5.

6. dry: as to adopt the method for airing, moisture: 30-35%.

9. vexed oil is opened fibre: (1) technical stipulation: interior temperature normal temperature, water 12%, compound oil Z-15 3.0%.(2) method of operating: first the fiber cake is joined in rotary drum, then add normal-temperature water and emulsification in advance grease completely, rotate 40min and get final product.

Embodiment 3

2. ease back, acidifying, enzyme process: (1) technical stipulation: water 200%, initial in temperature: normal temperature, penetrating agent JFC 0.5%, oxalic acid 5.0%, Treatment agent of compound enzyme skin sollagen F 0.40%.(2) method of operating: after mixing up liquor ratio, interior temperature, add penetrating agent JFC, oxalic acid, rotate 40min, add Treatment agent of compound enzyme skin sollagen F, rotate 90min, stop 60min, rotate 60min, open drum inspection, terminal pH=2.4 ±, interior temperature≤40 ℃.

3. neutralization: (1) technical stipulation: water 200%, 45 ℃ of interior temperature, sodium bicarbonate 1.5%.(2) method of operating: after mixing up liquor ratio, interior temperature, add sodium bicarbonate, rotate 120min, open drum inspection, terminal pH=5.0-6.5.

6. dry: as to adopt the method for airing, moisture: 30-35%.

9. vexed oil is opened fibre: (1) technical stipulation: interior temperature normal temperature, water 20%, compound oil Z-15 4.0%.(2) method of operating: first the fiber cake is joined in rotary drum,, adding normal-temperature water and emulsification in advance grease completely, rotate 60min and get final product.

Annotate: Treatment agent of compound enzyme skin sollagen F and compound oil Z-15 that the present invention is used produce by Chengdu Bailejin Biological Scinece ﹠ Technology Co., Ltd., and remaining chemical reagent is market and buys.

Claims

1. a method utilizing tanning chromium-containing by-products to prepare dermis collagen fibers is characterized in that the method contains the following steps:

(1) Weighing: Accurately weigh the chromium-containing secondary waste from tanning (hereinafter referred to as secondary waste) as the basis for counting the following processes;

(2) Softening, acidification, enzyme treatment: ①. Technical requirements: water 50-200%, initial internal temperature: room temperature, penetrant JFC 0.1-0.5%, oxalic acid 1.0-5.0%, compound enzyme skin collagen treatment agent F 0.10 -0.40%; ②. Operation method: After adjusting the liquid ratio and internal temperature, add penetrant JFC and oxalic acid, rotate for 10-40min, add compound enzyme skin collagen treatment agent F, rotate for 30-90min, stop for 10-60min, rotate 10-60min, drum inspection, end point pH=2.4±, internal temperature ≤40℃;

(3) Neutralization: ①. Technical requirements: 50-200% water, 30-45℃ internal temperature, 0.5-1.5% baking soda; ②. Operation method: After adjusting the liquid ratio and internal temperature, add baking soda and rotate 30-120min, drum inspection, end point pH=5.0-6.5;

(4) Out of the drum: After the neutralization meets the requirements, the auxiliary waste is discharged out of the drum, loaded into the car, and enters the fiberizing process;

(5) Defiberization and water squeezing: defibrate on the defibrating machine, and squeeze water directly after defibrating; the side waste is required to be completely deconstructed, without residual skin, and no foam is generated during the defibrating process; the fiber cake obtained after squeezing The moisture content is 60-70%;

(6) Drying: use the method of drying, moisture: 30-35%;

(7) Reversibility: After the moisture meets the requirements, collect and stack the fiber cake for 1-2 days to balance the moisture; note that the stacking time of the fiber cake should not exceed 10 days;

(8) Weighing: Accurately weigh the fiber cake as the basis for counting the following processes;

(9) Stuffed oil fiber opening: ①. Technical regulations: internal temperature, normal temperature, water 5-20%, compound oil Z-15 1.0-4.0%; ②. Operation method: first add the fiber cake into the drum, and then add Normal temperature water and fully emulsified oil in advance, just rotate for 10-60min;

(10) Out of the drum: After the oily fiber opening meets the requirements, the fluffy thick fiber is out of the drum, loaded into the car, and enters the next process;

(11) Opening: carried out on an opening machine; it is required to initially separate and loosen the entangled leather fibers;

(12) Fiber splitting: carried out on a fiber splitting machine; it is required to further separate and loosen the dermal collagen fibers without entanglement;

(13) Carding: Carry out on a carding machine; according to the separation and looseness of the dermal collagen fibers, card 1-2 times; the dermal collagen fibers are required to be loose and free of entanglement;

(14) Combing: It is carried out on a combing machine; according to the separation and looseness of the dermal collagen fibers, combing 1-3 passes to obtain dermal collagen fibers; the prepared dermal collagen fibers can reach the following technical performance indicators:

Appearance: light blue fibrous substance, no impurities seen by naked eyes;

Moisture (%): 18-25;

Linear density (dtex): 1.2-2.0;

Fiber length (mm): 20-30;

Breaking strength (cN/tex): ≥3.5;

Elongation at break (%): 10-30;

Moisture regain (%): 6-10.

2. according to the method for preparing dermis collagen fiber by utilization of the chromium-containing by-product of tanning according to claim 1, it is characterized in that the drum is a suspended wooden drum or a stainless steel drum.