From the Alderley & Wilmslow Advertiser - 10 May 1879:
Marriages
On the 5th inst, at the Parish Church, Rode Heath, by the Vicar, Mr James Knibbs, Tunstall, to Miss Mary Cotton. of Church Lawton.
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There is a slight conjecture that it may not have been this James who married Mary Ann Cotton.

Witnesses to the marriage were Henry and Harriet Shaw, Mary Ann's sister and brother-in-law who married a few years earlier.
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See James and Mary's Marriage Certificate

It's noted that James' surname is missing the "K" on the marriage certificate. but the announcement in the Alderley & Wilmslow Advertiser of the marriage on the 5th May is at odds with that.

There is a certain degree of conjecture that these notes apply to this particular James Knibbs, with the age and place of birth fluctuating tremendously in between 1851 and 1891. The theory is that James married twice and that his first wife Eliza was unwell after the birth of their son William/Walter. Maybe for this reason, James gave up his life on the canal boats and took alternative employment as a grocer so that he could care for them both.
In q1/1879 his first wife Eliza died and James remarried soon afterwards.
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It's frustrating that on both marriage certificates ages weren't specified other than "Full Age" which I believe normally meant over 21 years. However, for Mary Ann Cotton, I don't believe that was the case. The other frustration is that James is identified as "Bachelor" on both of them. The fact is that we are fairly confident that there was no other James who was also the son of Richard (deceased) who it could have been.
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We see James in 1881, living at Betchton, Congleton, Cheshire:
James Knibbs Head Mar 32 Chemical Labourer Tunstall Staffordshire
Mary A Knibbs Wife Mar 21 Wolverhalmpton Staffordshire
Walter Knibbs Son 10 Scholar Elton Cheshire
Emily Knibbs Daur 1 Wheelock Cheshire

So, in the census, James is recorded as being just 11 years older than Mary Ann, and then in 1901, just 5 years older - yet based on the ages and places of birth of his wife and daughter Emily, this is clearly the same family unit.

So, what links these facts to this James:
1. James was the son of Richard Knibbs, a boatman who died in 1865. The marriage certificates of James Knibs to Eliza Aston in 1867, and James Nibbs to Mary Ann Cotton in 1879, both identify the groom's father as Richard, deceased, and a boatman.
2. James Nibbs was living at Odd Rode, Staffordshire when he married for the second time in 1879. Fanny Wakefield (daughter of Richard Knibbs) was also living at Odd Rode in 1881.
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1867
We think it's probably this James Knibbs who married Eliza Aston in 1867 in Wolverhampton District, Staffordshire, England. FreeBMD and Ancestry.com have him transcribed as James Knibe from the marriage register.

The London Canal web site has the following from St. Mary's Church Marriage Register, Wolverhampton:

190 / 380 April 29 th. 1867
James Knibs F.A. Bach. Boatman on a boat son of Richard Knibs deceased
Eliza Aston F.A. Spin. on a boat dau.of Thomas Goodman Boatman
Witnessed by John Collins and Elizabeth Massey
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1869
From Sandbach Petty Sessions, 25 September 1869:
James Knibbs, beerseller of Moston, was committed to the House of Correction for one month, charged with stealing 80lbs weight of coals, at Moston on the 19th instant, the property of Messrs Hemer and Davis, salt proprietors of Wincham. The prisoner was captain of the boat Hugh belonging to Mr Croom, manager for the prosecutors, and on the day in question, he was on his way to Wincham with a boat load of slack, and while he had his boat tied up near to his own house, he was seen by a police officer stealing the coal from the boat and taking it towards his house.
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1870
The following newspaper article suggests that James was running a beerhouse for short while prior between 1867 and 1870, but for some reason his licence wasn't renewed.

From the Congleton & Macclesfield Mercury, and Cheshire General Advertiser - 03 September 1870:
Local and District Intelligence.
Middlewich. - On Monday llast the 29th inst., the general annual licensing meeting for the hundred of Northwich, in the county of Chester, was held at the Town Hall, in Middlewich. The Justices present were R. Wilbraham (chairman), G. W. Latham, C. H. France, A. Solly, J. Pearson, F. H. R. Wilbraham, W. R. Court, and E. Moss, Esqrss.
Alehouse licences : The whole of these licences, 139 in number. were. on the application of the parties interested, renewed, except the following, namely: James Charlesworth..........etc.,
Beerhouse Certificates Etc.,
The whole of these certificates, 82 in number, were, on the application of the several parties, renewed. except that of James Knibbs, of Moston, refused. William Burgess, Church Lawton, and Robert Siddall, Wharton, did not apply for a renewal. There were 17 new applications for certificates, which were supported by their respective advocates, all of which were refused except that of Charlas Skelleru, Buglawton (granted). The applications of James Eckersley, Northwich, and James Smallwood, Elton, were adjourned for further consideration until the 12th September next at Sandbach. The other business transacted was of the usual ordinary nature, and calls for no report thereof. The sessions lasted from 11 a. m. unit after 5 p. m.
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1871
We then suspect that it's this James who next appears with his wife Eliza living at the Grocer Shop in Moston, Cheshire in 1871 with a son named William. James is aged 27, Eliza 26 and William just 4 months. James' occupation is given as "Grocer".

There is no record of the birth of son William at the GRO, but there is a record of an Eliza Nibbs, born q4/1870 at Congleton District.
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1879
During q1/1879, and Eliza Knibbs dies in Walsall District, Staffordshire, aged just 34 years. We believe this is James' wife Eliza.

In q2/1879, a James Nibbs marries a girl named Mary Ann Cotton in Congleton District which sits on the border of Cheshire and Staffordshire.
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1881
Then in 1881, we see James Knibbs living at Malkins Bank, Betchton, Cheshire, England:
James KNIBBS Head M Male 32 Tunstall, Stafford, England Chemic Laborer
Mary A. KNIBBS Wife M Female 21 Wolverhampton
Walter KNIBBS Son Male 10 Elton, Cheshire, England Scholar
Emily KNIBBS Daur Female 1 Wheelock, Cheshire, England

Walter aged 10 years is the son of James and his first wife Eliza.
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1887
Walter Knibbs died in Congleton District in q2/1887 aged just 16.
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1891
In 1891 we see James and family living at Mill House, Wheelock, Cheshire::
James Knibbs Head M 46 Yard Foreman (Chemical) Cheshire Bumbury
Mary A Knibbs Wife M 31 Staffs Wolverhampton
Emily Knibbs Daur 11 Scholar Cheshire Sandbach
James Knibbs Son 10 Scholar Cheshire Sandbach
Edward Knibbs Daur 8 Scholar Cheshire Sandback
Beatrice Knibbs Son 2 Cheshire Sandbach

I note the the genders of Edward and Beatrice are the wrong way round.
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1901
In 1901, we see who we believe is James living at Mount Pl;easant, Wheelock, Cheshire.
James Knibbs Head M 47 Chemical Yard Foreman Bilston South Staffordshire
Mary Ann Knibbs wife M 42 Wolverhampton Staffordshire
Emily Knibbs Daur S 21 Wheelock Cheshire
James Knibbs Son S 19 Carter of Farm Malkins Bank Cheshire
Edward Knibbs Son S 18 Cowman oif Farm Malkins Bank Cheshire
Beatrice Knibbs Daur 12 School Girl Malkins Bank Cheshire
Sydney Knibbs Son 9 Wheelock Cheshire
Frederick Knibbs Son 7 Wheelock Cheshire
Elsie Knibbs Daur 5 Wheelock Cheshire
Harold Knibbs Son 4 Wheelock Cheshire
Leonard Knibbs Son 2 Wheelock Cheshire

In addition, I believe there were also the following children:
Alice Ann Knibbs, born Oct-Dec 1884, Congleton District (died Jan-Mar 1890 at Congleton District, age 5)
Percy Knibbs, born Apr-Jun 1890, Congleton District (died Jan-Mar 1891 at Congleton District, age 0)
Stanley Knibbs, born Oct-Dec 1898, Congleton District (I think it was him who died Jan-Mar 1899 at Congleton District, age 0)
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From the Directory of Cheshire, 1910:
Knibbs, James, farmer, Malkins' Bank,
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We see James and his family in 1911 living at Malkins Bank Farm, Betchton, Sandbach, Cheshire:
James Knibbs Head Married 57 Farmer Oxfordshire
Mary Ann Knibbs Wife Married (32 years) 53 Farmers Wife Staffordshire
Beatrice Knibbs Daughter Single 22 Domestic Duties at Home Betchton
Sydney Knibbs Son Single 19 Farmers Son Working on Farm Wheelock
Fred Knibbs Son Single 17 Apprentice to Smith Wheelock
Elsie Knibbs Daughter Single 15 Domestic Duties at Home
Harold Knibbs Son 14 Farmers Son Working on Farm Wheelock
Leonard Knibbs Son 12 School Wheelock
Kenneth Knibbs Son 8 School Betchton
Jessey Wainwright Man Servant 19 Labourer of Farm
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James Knibbs died in Congleton District q2/1926, aged 84.
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From the Alderley & Wilmslow Advertiser - 14 May 1926:
SANDBACH AND DISTRICT
Sunday, May 2nd.
Funeral late Mr. Jas. Knibbs (aged 84) of Malkins Bank Farm, took place at Christ Church, Wheelock, Tuesday May 4th.
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Read James' Last Will and Testament
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Knibbs James of Belchton near Sandbach Cheshire died 29 April 1926 Probate Chester 9 July to Sydney Knibbs and Harold Knibbs farmers Effects £1327 16s. 5d.

From the Manchester Evening News - 04 May 1907:
LOVER'S SAD END.
A verdict of found drowned was returned at Malkins Bank, Sandbach, yesterday, in the case of a young man named Edward Knibbs (24), a farmer's assistant, who was found drowned in a lock on the North Stafford Railway Canal, early on Thursday morning. After visiting his young lady at the Nag's Head Hotel, Wheelock, on Wednesday night. he left to return home at 11 30, and on nearing his home it is surmised that he was taking a short cut by the canal side when he fell into the lock. The night was dark and stormy, but how the the poor fellow got into the water will ever remain a mystery.The body was found by a lock attendant who was unable to open one of the gates, owing to the obstruction caused by the body. The deceased was well known and highly respected.

From the Crewe Chronicle - 23 April 1938:
SANDBACH
FUNERAL OF MR. S. KNIBBS.—The funeral of Mr. Sydney Knibbs, aged 44. of Malins Bank Farm took place on Saturday. when the Rev. B Pemberton conducted the service at Wheelock Church. At the house a short service was conducted by Mr. W. Brown, lay reader of Hassell Church. The mourners were Messrs Harold, Leonard, Kenneth, James, and Fred, brothers. Mrs. L. Ryder, Mrs. Gunn and Mrs. B. Darlington, sisters; Mr. J. B Gunn, Mr. B C. Ryder, Mr. H Darlington, Mrs. J. Knibbs, Mrs. K. Knibbs, Mrs. F. Knlbbs, and Miss S Beech, brothers-in-law and sisters-in-law; Messrs. W Pugh, F. Patin, H Smith, G Boulton, H B Bebbington, J. Hollins, T. Beard, H Wharton, R. Gorst, E Brown, H. Colelough, W Cadman, P. Jackson, H. Croxton, A. Hodgkinson, Mr and Mrs White, Miss G. Croston. and Mr. Hodgkinson. The bearers were Messrs H. Moulton, W Sutton, D. and C. Croxton, O. Barnett, and W. Tomkinson. The arrangements were carried out by Mr W. Chapman.
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Knibbs Sidney of Malkins Bank Sandbach Cheshire died 13 April 1938 Administration Chester 6 December to Harold Knibbs farmer Effects £260 10s. 8d.

I assume Harold named above is his brother Harold.

Leonard was born in the Congleton District which straddled the counties of Cheshire and Staffordshire. He was the only Leonard Knibbs in that are at the time, so I presume the following story relates to him:

From Staffordshire Sentinel - 9 September 1920:
Local Police Courts.
Stipendiary Court, Tunstall
Thursday:- Before Mr. W. Boulton (presiding) and Mr. H. Smallman.
DAMAGE TO LOCK.—Leonard Knibbs, a youth living in High street. Talke Pits. was summoned for committing damage to the extent of a shilling to a rabbit pen lock, the property of Thomas Newton, of Talke.—The complainant said about 11 p.m. on the 13th August. he heard noises in the garden, where his boys had a rabbit hutch. He went to see what. was the matter and striking a light found the defendant crouching behind some currant bushes. The rabbit hutch door had been forced open.—Defendant pleaded guilty and was ordered to pay £1 in all.
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Notice of Probate from The London Gazette, 8th March 1963:
Name of Deceased: Knibbs Leonard.
Address, Description and Date of Death: Malkins Bank Farm, Betchton, Sandbach, Cheshire, Farmer. 10th October 1960.
Notice of Claims to be given to: H. P. & H. C. Rigby, 31 Middlewich Road. Sandbach, Cheshire, Solicitors. (Kenneth Knibbs and Harold Knibbs.)
Date before which Claims are to be made: 10th May 1963
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Knibbs Leonard of Malkins Bank Farm Betchton near Sandbach Cheshire died 10 October 1960 Probate Chester 22 August to Kenneth Knibbs and Harold Knibbs farmers. Effects £1605 9s. 11d.

I believe Stanley and Leonard were twins. The GRO has it that Leonard died as an infant, but the 1901 census shows that Leonard was still alive so I suspect it was Stanley who died.